JP2011195828A - Benzofluoranthene-based polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound useful for manufacturing of a light-emitting element being excellent in maximum luminous efficiency.SOLUTION: The polymer compound includes a constitution unit represented by formula (1): wherein Aris an aromatic hydrocarbon group or an aromatic heterocyclic group; E is a group derived from formula (2) (R, R, R, R, R, R, R, R, Rand Rare each independently a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a group represented by -O-R, and these groups may have a substituent; Ris an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, these groups may have a substituent, and they may be the same or different when a plurality of Rs are present, and Rand R, Rand R, Rand R, Rand R, Rand R, Rand R, Rand R, Rand R, Rand R, and Rand Rmay be bonded to each other to form a ring).

Description

  The present invention relates to a benzofluoranthene polymer compound, a production method thereof, a polymer composition containing the same, a solution, an organic thin film, a light emitting element, a planar light source and a display device, and a raw material compound thereof.

  High-molecular-weight light-emitting materials and charge transport materials are variously studied because they are soluble in a solvent and can form an organic layer in a light-emitting element by a coating method. For example, a hole injection transport group, an electron As a polymer compound having a functional substituent such as an injection transport group or a light emitting group, polyfluorene having a triphenylaminediyl group introduced is known (see Non-Patent Document 1).

Advanced Materials; 2002, vol.11, p.809

  However, when the polymer compound is used as a light emitting material for a light emitting device, the maximum light emission efficiency has not been sufficient yet.

  Then, an object of this invention is to provide a high molecular compound useful for manufacture of the light emitting element which is excellent in maximum luminous efficiency. Another object of the present invention is to provide a polymer composition, a solution, an organic thin film, a light emitting element, a planar light source, and a display device containing the polymer compound. Another object of the present invention is to provide a method for producing the polymer compound and a compound useful for producing the polymer compound.

  The present invention first provides a polymer compound containing a structural unit represented by the following general formula (1).

［一般式（１）中、Ａｒ¹は、非置換若しくは置換の芳香族炭化水素基、又は、非置換若しくは置換の芳香族複素環基を示す。Ｅは、下記一般式（２）：

[In General Formula (1), Ar ¹ represents an unsubstituted or substituted aromatic hydrocarbon group or an unsubstituted or substituted aromatic heterocyclic group. E represents the following general formula (2):

（一般式（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁹、Ｒ⁹とＲ¹⁰、Ｒ¹とＲ⁸、及び、Ｒ¹⁰とＲ⁸は、互いに結合して、環を形成してもよい。）
で表される化合物における水素原子を１個取り除いてなる基を示す。ａａは、１以上の整数である。］

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A, which may have a substituent, and R ^A is an alkyl group, an aryl group, or , a monovalent aromatic heterocyclic group, when these groups which may have a substituent group .R ^a there are multiple, they may be different even in the same .R ¹ And R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁹ , R ⁹ and R ¹⁰ , R ¹ and R ⁸ and R ¹⁰ and R ⁸ may combine with each other to form a ring.)
The group formed by removing one hydrogen atom in the compound represented by this. aa is an integer of 1 or more. ]

R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁹ , R ⁹ and R ¹⁰ , R ¹ And R ⁸ and R ¹⁰ and R ⁸ are bonded to each other to form a ring, examples of the ring formed include an unsubstituted or substituted benzene ring. Examples of the substituent that the substituted benzene ring has include an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, and a group represented by —O—R ^A.

  Secondly, the present invention provides a compound represented by the following general formula (1M).

［一般式（１Ｍ）中、Ａｒ¹及びＥはそれぞれ独立に、前記と同じ意味を表す。Ｚ¹及びＺ²はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。ａａは、１以上の整数である。］

[In General Formula (1M), Ar ¹ and E each independently represent the same meaning as described above. Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. aa is an integer of 1 or more. ]

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ²⁷ (R ²⁷ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)

<Substituent group B>
—B (OR ²⁸ ) ₂ (R ²⁸ represents a hydrogen atom or an alkyl group. Two R ^{28 s} may be the same or different and may be bonded to each other to form a ring. . good), a group represented _{^{by, -BF 4 -. Q 1 (}} Q 1 is lithium, sodium, potassium, monovalent shows a cation) a group represented by the rubidium or cesium, -MgY ¹ (Y ¹ represents a chlorine atom, a bromine atom or an iodine atom), a group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn ( R ²⁹ ) ₃ (R ²⁹ represents a hydrogen atom or an alkyl group. The three R ^{29 s} may be the same or different and may combine with each other to form a ring.) A group represented by

  Third, the present invention provides a method for producing the polymer compound, the method comprising polymerizing a compound represented by the general formula (1M) and a compound represented by the following general formula (5M). A method for producing a molecular compound is provided.

［一般式（５Ｍ）中、Ｒ²²及びＲ²³はそれぞれ独立に、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。Ｚ³及びＺ⁴はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In General Formula (5M), R ²² and R ²³ each independently represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. . Z ³ and Z ⁴ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]

  Fourthly, the present invention provides a polymer composition containing the polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.

  Fifthly, the present invention provides a solution containing the polymer compound and a solvent.

  Sixth, the present invention provides an organic thin film containing the polymer compound or the polymer composition.

  Seventhly, this invention provides a light emitting element provided with the said organic thin film.

  Eighthly, the present invention provides a planar light source and a display device comprising the light emitting element.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element which is excellent in maximum luminous efficiency can be provided. In addition, a polymer composition, a solution, an organic thin film, a light-emitting element, a planar light source, and a display device including the polymer compound can be provided. Furthermore, a method useful for producing the polymer compound and a compound useful for producing the polymer compound can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  In the present specification, the “structural unit” means a unit structure present in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure existing two or more in the polymer compound). The “n-valent aromatic heterocyclic group” means an atomic group obtained by removing n hydrogen atoms directly bonded to an aromatic ring from an aromatic heterocyclic compound, and has a condensed ring structure Contains groups. “Heterocyclic compound” means not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom, etc. as atoms constituting a ring among organic compounds having a cyclic structure. The compound containing the hetero atom of these is meant. “Aromatic heterocyclic compound” means oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. A heterocyclic compound containing a heteroatom, wherein the heterocycle itself exhibits aromaticity, and a heterocycle containing a heteroatom such as phenoxazine, phenothiazine, dibenzothiophene, dibenzofuran, dibenzoborol, dibenzosilol, and benzopyran. Although the ring itself does not show aromaticity, it means a compound in which an aromatic ring is condensed to the heterocyclic ring. The “n-valent condensed aromatic heterocyclic group” represents a group having a condensed ring in the “n-valent aromatic heterocyclic group”. In the present specification, the aryl group does not include a group represented by E.

  In the present specification, in the structural formula, Me represents a methyl group, and Et represents an ethyl group.

<Polymer compound>
[First structural unit]
The polymer compound according to the present invention includes a structural unit represented by the general formula (1) (hereinafter referred to as “first structural unit”). This 1st structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

  In the general formula (1), aa is an integer of 1 or more, but is preferably 1 or 2 and more preferably 1 because the maximum luminous efficiency is more excellent. Note that the upper limit of aa is preferably 4 because the synthesis of the polymer compound is easy.

In the general formula (2), the alkyl group in R ^{1 to} R ¹⁰ may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, more preferably 1 to 12. The carbon number does not include the carbon number of the substituent. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, and 2-ethylhexyl. Group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like. The hydrogen atom in the alkyl group is an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O) —R. ^The group represented by ^A , the group represented by —C (═O) —O—R ^A , a cyano group or a fluorine atom may be substituted. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

In the general formula (2), the aryl group in R ^{1 to} R ¹⁰ is an atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from an aromatic hydrocarbon, and includes a group having a condensed ring. The aryl group usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 14 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-tetracenyl group, 2-tetracenyl group, 5-tetracenyl group, 1 -Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 1-biphenylyl group, 2-biphenylyl group, 2 -Phenanthrenyl group, 9-phenanthrenyl group, 6-chrycenyl group, 1-coronenyl group and the like can be mentioned. The hydrogen atom in the aryl group is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O ) ^A group represented by -R ^A , a group represented by -C (= O) -O-R ^A , a cyano group or a fluorine atom.

In general formula (2), the monovalent aromatic heterocyclic group in R ^{1 to} R ¹⁰ usually has 3 to 60 carbon atoms, and preferably 3 to 20 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the monovalent aromatic heterocyclic group include 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 2-thiazolyl group, 2-oxazolyl group, 2-thienyl group, 2-pyrrolyl group, 2-furyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 2-triazinyl group, 3-pyridazinyl group, 5-quinolyl group, 5-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group and the like can be mentioned. The hydrogen atom in the monovalent aromatic heterocyclic group is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , or a group represented by —S—R ^A. , -C (= O) -R ^A , a group represented by -C (= O) -O-R ^A , a cyano group, or a fluorine atom.

Examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group in R ^A include the same groups as those in R ¹ described above.

In the general formula (2), as the group represented by —O—R ^A in R ^{1 to} R ¹⁰ , when R ^A is an alkyl group, an alkoxy group having a linear, branched or cyclic alkyl group is Can be mentioned. The alkoxy group usually has 1 to 20 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, decyloxy group, and 3,7-dimethyl. Octyloxy group, dodecyloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, 2-methoxyethyloxy group, 2-ethoxy An ethyloxy group etc. are mentioned.

In the general formula (2), examples of the group represented by —O—R ^A in R ^{1 to} R ¹⁰ include an aryloxy group having usually 6 to 60 carbon atoms when R ^A is an aryl group. . Examples of the aryl group moiety include the same aryl groups represented by R ¹ described above. The aryloxy group is a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group ( "C ₁ -C ₁₂ alkoxy" means that the carbon number of the alkoxy moiety is 1 to 12, and so forth.) , C ₁ -C ₁₂ alkylphenoxy group (“C ₁ -C ₁₂ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms, the same shall apply hereinafter), 1-naphthyloxy group, 2- A naphthyloxy group, a pentafluorophenyloxy group, etc. are mentioned.

In the general formula (2), the group represented by —O—R ^A in R ^{1 to} R ¹⁰ has a carbon number of usually 3 to 60 when R ^A is a monovalent aromatic heterocyclic group. Yes, preferably 3-20 groups. Examples of the monovalent aromatic heterocyclic group include the same monovalent aromatic heterocyclic groups as those described above for R ¹ .

In the group obtained by removing one hydrogen atom from the compound represented by the general formula (2), R ⁹ and R ¹⁰ bonded to adjacent carbon atoms may form a ring together with the carbon atom.

In General formula (2), it is preferable that R < ¹ > -R < ⁶ >, R < ⁹ > -R < ¹⁰ > is a hydrogen atom, an alkyl group, or an aryl group.

In the general formula (2), R ⁷ and R ⁸ are more preferably an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and more preferably an aryl group.

In the case where E is a group formed by removing one hydrogen atom from the compound represented by the general formula (2), R ² , R ³ , R ⁴ in the compound represented by the general formula (2), It is preferably a group formed by removing one hydrogen atom from any one of the groups or atoms represented by R ⁵ , R ⁹ or R ^10. From the viewpoint of luminous efficiency and ease of monomer synthesis, It is more preferably a group formed by removing one hydrogen atom from any one of the groups or atoms represented by R ³ or R ⁴ in the compound represented by the general formula (2). From the viewpoint of ease of monomer synthesis, the compound is a group formed by removing one hydrogen atom from the group or atom represented by R ⁹ or R ¹⁰ in the compound represented by the general formula (2). Is more preferable. The group formed by removing one hydrogen atom from any one of the atoms (hydrogen atoms) represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁹ or R ¹⁰ is the above general formula ( It means a group in which any one of R ² , R ³ , R ⁴ , R ⁵ , R ⁹ or R ¹⁰ in 2) is a single bond.

  Examples of the group formed by removing one hydrogen atom from the compound represented by the general formula (2) include a group represented by the following general formula (2-1).

［一般式（２−１）中、複数あるＸのうち、１個は、結合手を示し、その他は、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示す。Ｒ^Xは、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。複数あるＸ、Ｒ^Xは、各々、同一であっても異なっていてもよい。Ｒ^Aは前記と同じ意味を表す。］

[In General Formula (2-1), one of a plurality of X represents a bond, and the other represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or -O. a group represented by -R ^a. R ^X represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or a group represented by —O—R ^A , and these groups optionally have a substituent. . A plurality of X and R ^X may be the same or different. R ^A represents the same meaning as described above. ]

In the group formed by removing one hydrogen atom from the compound represented by the general formula (2), R ⁹ and R ¹⁰ bonded to adjacent carbon atoms form a ring together with the carbon atom. Is, for example, a group formed by removing one hydrogen atom from the compound represented by the following general formula (3) or the following general formula (8), and has excellent luminous efficiency and facilitates monomer synthesis. And a group formed by removing one hydrogen atom from a compound represented by the following general formula (3), a group formed by removing one hydrogen atom from a compound represented by the following general formula (3), A group having 24 or less carbon atoms constituting the fluoranthene ring is more preferable. In the following formula (3), R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ¹ and R ⁸ Are bonded to each other to form a ring, “the number of carbon atoms constituting the benzofluoranthene ring” includes the number of carbon atoms of these rings.

［一般式（３）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、及び、Ｒ¹とＲ⁸は、互いに結合して、環を形成してもよい。Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは、前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。］

[In general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic group. A heterocyclic group or a group represented by —O—R ^A is shown, and these groups may have a substituent. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ¹ and R ⁸ are bonded to each other, A ring may be formed. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or a group represented by —O—R ^A , This group may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ]

［一般式（８）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、及び、Ｒ¹とＲ⁸は、互いに結合して、環を形成してもよい。Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹及びＲ³²はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは、前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。］

[In General Formula (8), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic group. A heterocyclic group or a group represented by —O—R ^A is shown, and these groups may have a substituent. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ¹ and R ⁸ are bonded to each other, A ring may be formed. R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are each independently represented by a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or —O—R ^A. These groups may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ]

In the case where E is a group formed by removing one hydrogen atom from the compound represented by the general formula (3), R ² , R ³ , R ⁴ in the compound represented by the general formula (3), A group formed by removing one hydrogen atom from any one of the groups or atoms represented by R ⁵ , R ^12, or R ¹³ is preferable, because it has excellent luminous efficiency and facilitates monomer synthesis. And a group formed by removing one hydrogen atom from any one of the groups or atoms represented by R ³ , R ⁴ , R ¹² or R ¹³ in the compound represented by the general formula (3). More preferred. In the compound represented by the general formula (3), one hydrogen atom is selected from any one of the atoms (hydrogen atoms) represented by R ² , R ³ , R ⁴ , R ⁵ , R ¹² or R ^13. The group obtained by removing the individual means a group in which any one of R ² , R ³ , R ⁴ , R ⁵ , R ¹² or R ^{13 in} the general formula (3) is a single bond.

In the general formula (3), R ⁷ and R ⁸ are preferably an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and are an aryl group, because of their excellent luminous efficiency and durability. It is more preferable.

  Examples of the compound represented by the general formula (3) include a group formed by removing one hydrogen atom from a compound represented by the following general formula (3-1).

［一般式（３−１）中、複数あるＸのうち、１個は、結合手を示し、その他は、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Xは、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。複数あるＸ及びＲ^Xは、各々、同一であっても異なっていてもよい。Ｒ^Aは前記と同じ意味を表す。］

[In General Formula (3-1), one of a plurality of X represents a bond, and the other represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or -O. a group represented by -R ^a, these groups may have a substituent. R ^X represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or a group represented by —O—R ^A , and these groups optionally have a substituent. . A plurality of X and R ^X may be the same or different. R ^A represents the same meaning as described above. ]

  Examples of the compound represented by the general formula (2) include compounds represented by the following formulas (1-001) to (1-061).

In the formula (1), Ar ¹ represents an unsubstituted or substituted aromatic hydrocarbon group or an unsubstituted or substituted aromatic heterocyclic group. Examples of the substituent include an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, and a group represented by —O—R ^A.
Carbon number of the said aromatic hydrocarbon group is 6-60 normally, Preferably it is 6-48, More preferably, it is 6-20, More preferably, it is 6-14. The aromatic hydrocarbon group is a (2 + aa) valent aromatic hydrocarbon group, preferably a trivalent or tetravalent aromatic hydrocarbon group, and more preferably a trivalent aromatic hydrocarbon group.
The aromatic heterocyclic group has usually 3 to 60 carbon atoms, preferably 3 to 20 carbon atoms. The aromatic heterocyclic group is a (2 + aa) -valent aromatic heterocyclic group, preferably a trivalent or tetravalent aromatic heterocyclic group, and more preferably a trivalent aromatic heterocyclic group.

In the general formula (1), Ar ¹ is preferably an unsubstituted or substituted aromatic hydrocarbon group, more preferably a trivalent or tetravalent aromatic hydrocarbon group, because of its excellent luminous efficiency and durability. A trivalent aromatic hydrocarbon group is more preferable. The “n-valent aromatic hydrocarbon group” means an atomic group obtained by removing n hydrogen atoms directly bonded to an aromatic ring from an aromatic hydrocarbon, and includes a group having a condensed ring structure.

  Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 1-tetracene, pyrene, perylene, fluorene, phenanthrene, chrysene, coronene, and the like.

  As the structural unit represented by the general formula (1), the structural unit represented by the following general formula (4) is preferable because the luminous efficiency and durability are excellent and the synthesis of the polymer compound is facilitated. .

［一般式（４）中、Ｒ¹⁵は、水素原子、アルキル基、アリール基、１価の芳香族複素環基、−Ｏ−Ｒ^Aで表される基、又は、Ｅで表される基を示し、これらの基は置換基を有していてもよい。Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰及びＲ²¹はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。Ｒ¹⁷とＲ¹⁸、及び、Ｒ¹⁹とＲ²⁰は、互いに結合して、環を形成してもよい。Ｅは、前記と同じ意味を有する。］

[In General Formula (4), R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , or a group represented by E. And these groups may have a substituent. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently represented by a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or —O—R ^A. These groups may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a ring. E has the same meaning as described above. ]

In the formula (4), R ¹⁵ is preferably an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group.

In the formula (4), R ¹⁶ , R ¹⁷ , R ²⁰ and R ²¹ are preferably hydrogen atoms, and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are hydrogen atoms. Is more preferable.

In the formula (4), since the luminous efficiency and durability are excellent, R ¹⁵ is an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and R ¹⁶ , R ¹⁷ , R ²⁰ and R ²¹ is preferably a hydrogen atom, R ¹⁵ is an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R More preferably, ²⁰ and R ²¹ are hydrogen atoms.

  As the structural unit represented by the formula (1), since the luminous efficiency and durability are excellent, the structural units represented by the following formulas (1-101) to (1-114) are preferable.

［式中、Ｒは、水素原子、アルキル基、アリール基、１価の芳香族複素環基、−Ｏ−Ｒ^Aで表される基、−Ｓ−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｏ−Ｒ^Aで表される基、シアノ基又はフッ素原子を示す。アルキル基、アリール基、１価の芳香族複素環基、−Ｏ−Ｒ^Aで表される基、−Ｓ−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｒ^Aで表される基、及び、−Ｃ（＝Ｏ）−Ｏ−Ｒ^Aで表される基は、置換基を有していてもよい。Ｒ^aは、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。Ｅは、前記と同じ意味を表す。複数あるＲは同一であっても異なっていてもよい。複数あるＲ^aは、同一であっても異なっていてもよい。Ｒ^Aは前記と同じ意味を表す。］

[Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , —C ( ^A group represented by ═O) —R ^A , a group represented by —C (═O) —O—R ^A , a cyano group, or a fluorine atom; An alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , and a group represented by —C (═O) —R ^A The group and the group represented by —C (═O) —O—R ^A may have a substituent. R ^a represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. E represents the same meaning as described above. A plurality of R may be the same or different. A plurality of ^Ra may be the same or different. R ^A represents the same meaning as described above. ]

[Second structural unit]
Since the polymer compound according to the present invention is excellent in luminous efficiency and durability, it preferably contains a structural unit represented by the following general formula (5) (hereinafter referred to as “second structural unit”).

［一般式（５）中、Ｒ²²及びＲ²³はそれぞれ独立に、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。なお、Ｒ²²及びＲ²³は、Ｅで表される基とは異なる。］

[In General Formula (5), R ²² and R ²³ each independently represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. . R ²² and R ²³ are different from the group represented by E. ]

In the general formula (5), examples of the alkyl group in R ²² and R ²³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a pentyl group, a 2-methylbutyl group, Examples include isoamyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like. These groups may have a substituent.

In the general formula (5), examples of the aryl group in R ²² and R ²³ include an unsubstituted or substituted phenyl group, an unsubstituted or substituted 1-naphthyl group, and an unsubstituted or substituted 2-naphthyl group. .

In the general formula (5), the monovalent aromatic heterocyclic group in R ²² and R ²³ is the same as the group described and exemplified for the monovalent aromatic heterocyclic group in R ¹ described above.

In the general formula (5), R ²² and R ²³ are substituted or unsubstituted aryl groups or substituted or unsubstituted alkyl groups because the polymer compound according to the present invention has excellent heat resistance and solubility. An unsubstituted aryl group; an aryl group substituted with an alkyl group, an alkoxy group, an aryl group or a substituted amino group; an unsubstituted alkyl group; an alkyl group, an alkoxy group, an aryl group or a substituted amino group; A substituted alkyl group is more preferable, and 4-tolyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 4- (3,7-dimethyloctyl) phenyl group, 3-tolyl group, 3-butylphenyl group, 3-tert-butylphenyl group, -Hexylphenyl group, 3-octylphenyl group, 3- (2-ethylhexyl) phenyl group, 3- (3,7-dimethyloctyl) phenyl group, 3,5-dimethylphenyl group, 3,5-di- (tert -Butyl) phenyl group, 3,5-dihexylphenyl group, 3,5-dioctylphenyl group, 3,4-dihexylphenyl group, 3,4-dioctylphenyl group, 4-hexyloxyphenyl group, 4-octyloxyphenyl Group, 4- (2-ethoxy) ethoxyphenyl group, 4- (4′-tert-butylbiphenylyl) group, 9,9-dihexylfluoren-2-yl group, 9,9-dioctylfluoren-2-yl group Pentyl group, neopentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, 3,7-dimethyloctyl group, Group, decyl group, dodecyl group, 2-ethyldecyl group, or 4-butyl-octyl group is more preferable.

  This 2nd structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

[3rd structural unit]
Since the polymer compound according to the present invention has excellent durability, the following general formula (6):

［一般式（６）中、Ａｒ²は、アリーレン基、２価の芳香族複素環基、又は、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を示す。Ａｒ²は、アルキル基、アリール基、１価の芳香族複素環基、−Ｏ−Ｒ^Aで表される基、−Ｓ−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｏ−Ｒ^Aで表される基、−Ｎ（Ｒ^A）₂で表される基、シアノ基、及び、フッ素原子からなる群より選ばれる少なくとも１個の置換基を有していてもよい。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。なお、式（６）で表される構成単位は、前記式（１）、（５）で表される構成単位とは異なる。］
で表される構成単位（以下、「第３構成単位」と言う。）を含むことが好ましい。

[In General Formula (6), Ar ² is an arylene group, a divalent aromatic heterocyclic group, or two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group. A linked divalent group is shown. Ar ² represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O) —R ^A. At least selected from the group consisting of: a group represented by —C (═O) —O—R ^A , a group represented by —N (R ^A ) ₂ , a cyano group, and a fluorine atom. It may have one substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. The structural unit represented by the formula (6) is different from the structural units represented by the formulas (1) and (5). ]
Is preferably included (hereinafter referred to as “third structural unit”).

In the general formula (6), the group represented by —S—R ^A may be linear, branched or cyclic, an alkylthio group having 1 to 20 carbon atoms, and usually 6 to 60 carbon atoms. Of the arylthio group.

In the general formula (6), the group represented by —C (═O) —R ^A may be linear, branched or cyclic, and is usually an alkylcarbonyl group having 1 to 20 carbon atoms, carbon An arylcarbonyl group whose number is usually 6 to 60 is mentioned.

In the general formula (6), the group represented by —C (═O) —O—R ^A may be linear, branched or cyclic, and is usually an alkyloxycarbonyl having 1 to 20 carbon atoms. Examples thereof include an aryloxycarbonyl group usually having 6 to 60 carbon atoms.

In the general formula (6), the group represented by —N (R ^A ) ₂ is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 60 carbon atoms. And an amino group substituted with two groups.

In the general formula (6), the arylene group in Ar ² generally has 6 to 60 carbon atoms, preferably 6 to 48, more preferably 6 to 30, and still more preferably 6 to 14. . The carbon number does not include the carbon number of the substituent. Examples of the arylene group include 1,4-phenylene group (formula (6-001)), 1,3-phenylene group (formula (6-002)), and 1,2-phenylene group (formula (6-003)). Phenylene group such as naphthalene-1,4-diyl group (formula (6-004)), naphthalene-1,5-diyl group (formula (6-005)), naphthalene-2,6-diyl group (formula ( 6-006)), naphthalenediyl groups such as naphthalene-2,7-diyl group (formula (6-007)); 4,5-dihydrophenanthrene-2,7-diyl group (formula (6-008)) A fluorene-3,6-diyl group (formula (6-009)); a benzofluorenediyl group represented by formulas (6-010) to (6-012); anthracene-2,6 -Diyl group (formula (6-013)), a Like anthracene-diyl groups such as anthracene-9,10-diyl group (formula (6-014)) and the like. The hydrogen atom in these arylene groups is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , —C (= O) a group represented by -R ^A , a group represented by -C (= O) -O-R ^A , a group represented by -N (R ^A ) ₂ , a cyano group or a fluorine atom. May be.

［式（６−００１）〜（６−０１４）中、Ｒ及びＲ^aはそれぞれ独立に、前記と同じ意味を表す。］

[In the formulas (6-001) to (6-014), R and R ^a each independently represent the same meaning as described above. ]

In the general formula (6), the divalent aromatic heterocyclic group for Ar ² is preferably a divalent condensed aromatic heterocyclic group because the polymer compound according to the present invention is excellent in stability. This divalent condensed aromatic heterocyclic group usually has 8 to 60 carbon atoms, preferably 8 to 20 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the divalent condensed aromatic heterocyclic group include quinolinediyl groups such as quinoline-2,6-diyl group (formula (6-101)); isoquinoline-1,4-diyl group (formula (6-102)) Isoquinolinediyl group such as quinoxaline-5,8-diyl group (formula (6-103)), etc .; carbazole-3,6-diyl group (formula (6-104)), carbazole-2,7 A carbazole diyl group such as a diyl group (formula (6-105)); a dibenzofuran-4,7-diyl group (formula (6-106)), a dibenzofuran-3,8-diyl group (formula (6-107)) A dibenzothiophene diyl group such as a dibenzothiophene-4,7-diyl group (formula (6-108)), a dibenzothiophene-3,8-diyl group (formula (6-109)); Benzosilol-4,7-diyl group (formula (6-110)), dibenzosilol-3,8-diyl group (formula (6-111)) and the like; phenoxazine-3,7-diyl group (Formula (6-112)), phenoxazine diyl group such as phenoxazine-2,8-diyl group (formula (6-113)); phenothiazine-3,7-diyl group (formula (6-114)), A phenothiazine diyl group such as a phenothiazine-2,8-diyl group (formula (6-115)); a dihydroacridine diyl group such as a dihydroacridine-2,7-diyl group (formula (6-116)); 117) and the like. The hydrogen atom in these divalent fused aromatic heterocyclic groups is represented by an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , or —S—R ^{A. A} group represented by —C (═O) —R ^A , a group represented by —C (═O) —O—R ^A , a cyano group, or a fluorine atom.

［式（６−１０１）〜（６−１１７）中、Ｒ及びＲ^aはそれぞれ独立に、前記と同じ意味を表す。］

[In the formulas (6-101) to (6-117), R and R ^a each independently represent the same meaning as described above. ]

In the general formula (6), the divalent group in which two or more groups of the same or different species selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group in Ar ² are connected usually has 4 carbon atoms. ~ 60, preferably 12 ~ 60. The carbon number does not include the carbon number of the substituent. Examples of such a group include groups represented by the following formulas (6-201) to (6-208).

［式（６−２０１）〜（６−２０８）中、Ｒは、前記と同じ意味を表す。］

[In formulas (6-201) to (6-208), R represents the same meaning as described above. ]

In the formula (6), Ar ² is a 1,4-phenylene group (formula) because the chemical stability of the polymer compound according to the present invention and the luminous efficiency of the light-emitting device using the polymer compound are excellent. (6-001)), 1,3-phenylene group (formula (6-002)), 9,10-dihydrophenanthrene-2,7-diyl group (formula (6-008)), fluorene-3,6- A diyl group (formula (6-009)), a benzofluorenediyl group represented by formulas (6-010) to (6-012), an anthracene-2,6-diyl group (formula (6-013)), Anthracene-9,10-diyl group (formula (6-014)), carbazole-3,6-diyl group (formula (6-104)), carbazole-2,7-diyl group (formula (6-105)) , Dibenzofuran-4,7-diyl group (formula (6-106)) Dibenzofuran-3,8-diyl group (formula (6-107)), dibenzothiophene-4,7-diyl group (formula (6-108)), dibenzothiophene-3,8-diyl group (formula (6-109) )), Dibenzosilol-4,7-diyl group (formula (6-110)), dibenzosilol-3,8-diyl group (formula (6-111)), phenoxazine-3,7-diyl group (formula (6-112)), phenothiazine-3,7-diyl group (formula (6-114)), dihydroacridine-2,7-diyl group (formula (6-116)), and formula (6-117). A divalent group represented by formula (6-201), a divalent group represented by formula (6-202), a divalent group represented by formula (6-207) Groups are preferred, in which R is a hydrogen atom, an alkyl group, an aryl group or 1 It is more preferably a valent aromatic heterocyclic group (particularly a hydrogen atom or an alkyl group), and R ^a is an alkyl group or an aryl group.

  This 3rd structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

[Fourth structural unit]
Since the polymer compound according to the present invention is excellent in luminous efficiency and durability of a light emitting device obtained using the polymer compound, the following general formula (7):

［一般式（７）中、Ａｒ³、Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、非置換若しくは置換のアリーレン基、非置換若しくは置換の２価の芳香族複素環基、又は、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。Ａｒ³とＡｒ⁴、Ａｒ³とＡｒ⁶、及び、Ａｒ⁴とＡｒ⁵は、それぞれ、単結合して、又は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（Ｒ^A）−、−Ｃ（＝Ｏ）−Ｎ（Ｒ^A）−若しくは−Ｃ（Ｒ^A）₂−で表される基を介して結合して、環を形成してもよい。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。Ｒ²⁴、Ｒ²⁵及びＲ²⁶はそれぞれに独立に、水素原子、アルキル基、アリール基、１価の複素環基、又は、アリールアルキル基を表し、これらの基は置換基を有していてもよい。ａは０〜３の整数を示し、ｂは０又は１を示す。］
で表される構成単位（以下、「第４構成単位」と言う。）を含むことが好ましい。

[In the general formula (7), Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group. And a divalent group in which two or more identical or different groups selected from the group consisting of divalent aromatic heterocyclic groups are linked. Ar ³ and Ar ⁴ , Ar ³ and Ar ⁶ , and Ar ⁴ and Ar ⁵ are each a single bond, or —O—, —S—, —C (═O) —, —C (= O) -O -, - N ( R a) -, - C (= O) -N (R a) - or -C (R ^a) ₂ - a bond to via a group represented by the ring It may be formed. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group, and these groups may have a substituent. Good. a represents an integer of 0 to 3, and b represents 0 or 1. ]
Is preferably included (hereinafter referred to as “fourth structural unit”).

“Ar ³ and Ar ⁴ , Ar ³ and Ar ⁶ , and Ar ⁴ and Ar ⁵ are each a single bond” means Ar ³ and Ar ⁴ , Ar ³ and Ar ⁶ , and Ar ⁴ and Ar ^5. Each means a direct bond.

In the general formula (7), the arylene group in Ar ³ , Ar ⁴ , Ar ^5, and Ar ⁶ is described as a group represented by the following formula (6-301) and the above-described arylene group in Ar ² . The thing similar to the illustrated group is mentioned.

［式（６−３０１）中、Ｒ及びＲ^aはそれぞれ独立に、前記と同じ意味を表す。］

[In the formula (6-301), R and R ^a each independently represent the same meaning as described above. ]

In the general formula (7), as the divalent aromatic heterocyclic group in Ar ³ , Ar ⁴ , Ar ⁵ and Ar ^6, the groups explained and exemplified as the divalent aromatic heterocyclic group in Ar ² described above It is the same.

In the general formula (7), a divalent group in which two or more groups of the same or different species selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group in Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are connected. The group of represents the same meaning as described above, but also includes a group in which the groups represented by the formula (6-301) are combined.

In the general formula (7), the group represented by Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ is an unsubstituted or substituted arylene group, and the stability of the polymer compound of the present invention is good. In addition, a light emitting device using the polymer compound is more preferable because it is more excellent in luminous efficiency.

In the general formula (7), R ²⁴ , R ²⁵ and R ²⁶ are an alkyl group, because the stability of the polymer compound according to the present invention and the luminous efficiency of the light emitting device using the polymer compound are excellent. An aryl group or a monovalent aromatic heterocyclic group is preferable, and an aryl group is more preferable.

In the general formula (7), when Ar ³ and Ar ⁴ , Ar ³ and Ar ⁶ , Ar ⁴ and Ar ⁵ are bonded to each other to form a ring, the ring is usually a 5- to 7-membered member. It is a ring.

  As the structural unit represented by the general formula (7), structural units represented by the following formulas (7-001) to (7-005) are preferable.

［式（７−００１）〜（７−００５）中、Ｒ及びＲ^aはそれぞれ独立に、前記と同じ意味を表す。］

[In the formulas (7-001) to (7-005), R and R ^a each independently represent the same meaning as described above. ]

As the structural unit represented by the general formula (7), the stability of the polymer compound according to the present invention and the light emitting efficiency of the light-emitting element using the polymer compound are excellent. Therefore, the formula (7-001) ) To (7-005) is a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group (in particular, a hydrogen atom or an alkyl group), and R ^a is The structural unit which is an alkyl group or an aryl group is preferable.

  This 4th structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

As the polymer compound according to the present invention, from the viewpoint of durability,
A first structural unit represented by the general formula (1);
A polymer compound containing the second structural unit represented by the general formula (5) is preferable.

As the polymer compound according to the present invention, from the viewpoint of luminous efficiency and durability,
A first structural unit represented by the general formula (1);
A second structural unit represented by the general formula (5);
A polymer compound containing a third structural unit represented by the general formula (6) and at least one structural unit selected from the group consisting of the fourth structural unit represented by the general formula (7) is preferable.
A first structural unit represented by the general formula (1);
A second structural unit represented by the general formula (5);
A polymer compound containing the fourth structural unit represented by the general formula (7) is more preferable.

  The polymer compound according to the present invention is preferably a conjugated polymer compound because the light emitting device obtained using the polymer compound has excellent luminous efficiency.

[Configuration of Polymer Compound According to the Present Invention]
Since the polymer compound according to the present invention is excellent in luminous efficiency of a light-emitting device obtained using the polymer compound, the content of the first constituent unit is such that the first constituent unit, the second constituent unit, The total content of the third structural unit and the fourth structural unit is preferably 0.01 to 90 mol%, more preferably 0.1 to 50 mol%, and more preferably 0.1 to 20 mol%. More preferably, it is mol%, and particularly preferably 0.5 to 10 mol%.

  Since the polymer compound according to the present invention is excellent in luminous efficiency of a light-emitting device obtained using the polymer compound, the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. The total content of is preferably 80 to 100% by weight, more preferably 90 to 100% by weight, based on the total amount of the polymer compound.

  When the polymer compound according to the present invention contains the fourth structural unit, the content of the fourth structural unit is that of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. The total content is preferably 0.5 mol% or more, and more preferably 1 mol% or more. Moreover, since the luminous efficiency and durability are excellent, the upper limit of the content is preferably 20 mol%, and more preferably 10 mol%.

  Examples of the polymer compound according to the present invention include polymer compounds P1 to P20 obtained by combining the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. Here, the total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit in the polymer compounds P1 to P20 is 100% by weight based on the total amount of the polymer compound.

  In the polymer compound according to the present invention, if the polymerization active group remains as it is in the terminal group, the light emitting characteristics and life of the light emitting device produced using the polymer compound may be lowered. Therefore, the terminal group is preferably a stable group (for example, an aryl group or a monovalent aromatic heterocyclic group).

  The polymer compound of the present invention may be any copolymer, for example, any of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and the like.

  The polymer compound according to the present invention is useful as a light-emitting material, a charge transport material, and the like. When used, the polymer compound may be used in combination with other compounds and used as a polymer composition described below.

The number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound according to the present invention is usually 1 × 10 ³ to 1 × 10 ⁸ , preferably Is 1 × 10 ⁴ to 1 × 10 ⁶ .

The polymer compound according to the present invention has a polystyrene-equivalent weight average molecular weight (Mw) of usually 1 × 10 ³ to 1 × 10 ⁸ , and film-formability and light emission of a light-emitting element obtained from the polymer compound. Since efficiency is excellent, it is preferably 1 × 10 ^{4 to} 5 × 10 ⁶ .

  Since the durability against various processes for producing a light emitting element or the like, the stability due to heat generation during driving of the light emitting element, and the heat resistance are improved, the glass transition temperature of the polymer compound according to the present invention is 70. It is preferable that the temperature is higher than 100 ° C., more preferably higher than 100 ° C.

<Method for producing polymer compound>
The polymer compound according to the present invention may be produced by any method. Preferred embodiments will be described below.

  When the polymer compound according to the present invention is a polymer compound containing the first structural unit represented by the general formula (1) and the second structural unit represented by the general formula (5), The polymer compound is prepared by dissolving a compound represented by the following general formula (1M) and a compound represented by the following general formula (5M) in an organic solvent as necessary to obtain an alkali or an appropriate catalyst or ligand. It can manufacture by the method including the process superposed | polymerized by polymerization methods, such as well-known aryl-aryl coupling using the compound used as this.

［一般式（１Ｍ）中、Ａｒ¹及びＥはそれぞれ独立に、前記と同じ意味を表す。Ｚ¹及びＺ²はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれるいずれかの基を示す。ａａは、１以上の整数である。］

[In General Formula (1M), Ar ¹ and E each independently represent the same meaning as described above. Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. aa is an integer of 1 or more. ]

［一般式（５Ｍ）中、Ｒ²²及びＲ²³はそれぞれ独立に、前記と同じ意味を表す。Ｚ³及びＺ⁴はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In General Formula (5M), R ²² and R ²³ each independently represent the same meaning as described above. Z ³ and Z ⁴ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]

  The polymer compound according to the present invention is represented by the first structural unit represented by the general formula (1), the second structural unit represented by the general formula (5), and the following general formula (6). The at least one structural unit selected from the group consisting of the third structural unit and the fourth structural unit represented by the following general formula (7): A compound represented by (1M), a compound represented by the general formula (5M), a compound represented by the following general formula (6M) and / or a compound represented by the following general formula (7M) , And if necessary, it is prepared by a method including a step of copolymerizing by a known polymerization method such as aryl-aryl coupling using a compound that becomes an alkali, an appropriate catalyst, or a ligand, dissolved in an organic solvent. Can do.

［一般式（６Ｍ）中、Ａｒ²は前記と同じ意味を表す。Ｚ⁵及びＺ⁶はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれる基を示す。］

[In General Formula (6M), Ar ² represents the same meaning as described above. Z ⁵ and Z ⁶ each independently represent a group selected from the group consisting of the substituent group A and the substituent group B. ]

［一般式（７Ｍ）中、Ａｒ³、Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、前記と同じ意味を表す。Ｚ⁷及びＺ⁸はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれる基を示す。］

[In the general formula (7M), Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ each independently represent the same meaning as described above. Z ⁷ and Z ⁸ each independently represent a group selected from the group consisting of the substituent group A and the substituent group B. ]

Examples of the alkyl group in R ²⁷ , R ²⁸ and R ²⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a pentyl group, a 2-methylbutyl group, an isoamyl group, and a hexyl group. , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group, and the like, and these groups may have a substituent. Carbon number of these alkyl groups is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

The aryl group in R ²⁷ is the same as the group explained and exemplified as the aryl group in R ¹ in the general formula (2). However, the synthesis becomes easy and the reactivity during polymerization becomes good. , Phenyl group, 4-tolyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group and 4-trifluoromethylphenyl group are preferable.

Examples of the group represented by —O—S (═O) ₂ R ²⁷ include a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a phenylsulfonyloxy group, a 4-methylphenylsulfonyloxy group, and 4-trifluoromethylphenylsulfonyl. An oxy group etc. are mentioned.

Examples of the group represented by —B (OR ²⁸ ) ₂ include groups represented by the following formulas.

The group represented by _{^{Q 1, -BF 4 - - -BF}} 4 K + and the like.

Examples of the group represented by —Sn (R ³⁶ ) ₃ include a trimethylstannyl group, a triethylstannyl group, and a tributylstannyl group.

In the general formula (5M), Z ³ and Z ⁴ each independently represent a group selected from the group consisting of the substituent group A and the following substituent group B,
When Z ¹ and Z ² in the general formula (1M) are both groups selected from the substituent group A, at least one of Z ³ and Z ⁴ is a group selected from the substituent group B;
When both Z ¹ and Z ² in the general formula (1M) are groups selected from the substituent group B, at least one of Z ³ and Z ⁴ is a group selected from the substituent group A.

  The compound represented by the general formula (1M), the compound represented by the general formula (5M), the compound represented by the general formula (6M) and the compound represented by the general formula (7M) are: Those previously synthesized and isolated may be used, or synthesized in the reaction system and used as they are. When the obtained polymer compound is used for a light emitting device, the purity tends to affect the performance of the light emitting device. Therefore, these compounds are preferably purified by methods such as distillation, sublimation purification, and recrystallization.

  Examples of the polymerization method include a polymerization method by Suzuki coupling reaction (Chem. Rev., Vol. 95, pages 2457-2483 (1995)), a polymerization method by Grignard reaction (Bull. Chem. Soc.Jpn., 51, 2091 (1978)), a method of polymerizing with Ni (0) catalyst (Progress in Polymer Science, 17, 1153-1205, 1992) And a method using a Stille coupling reaction (European Polymer Journal, Vol. 41, pages 2923-2933 (2005)). Among these, the method of polymerizing by Suzuki coupling reaction and the method of polymerizing by Ni (0) catalyst are preferable because the synthesis of raw materials is easy and the polymerization reaction operation is simple, and the structure control of the polymer compound is preferable. Therefore, a method of polymerizing by an aryl-aryl cross-coupling reaction such as a Suzuki coupling reaction, a Grignard reaction, or a Stille coupling reaction is more preferable, and a method of polymerizing by a Suzuki coupling reaction is particularly preferable.

As a group selected from the group consisting of the substituent group A and the substituent group B, an appropriate group may be selected according to the kind of the polymerization reaction, but when selecting a method of polymerization by Suzuki coupling reaction, Since the synthesis is simple and each compound is easy to handle, the group selected from the substituent group A is preferably a chlorine atom, bromine atom, or iodine atom, more preferably a bromine atom, and a group selected from the substituent group B Is preferably a group represented by —B (OR ²⁸ ) ₂ .

  The polymerization method includes the compound represented by the general formula (1M), the compound represented by the general formula (5M), the compound represented by the general formula (6M) and / or the general formula. The method of making the compound represented by (7M) react with a suitable catalyst and a base as needed is mentioned. When selecting a polymerization method by Suzuki coupling reaction, in order to obtain a polymer compound having a desired molecular weight, the compound represented by the general formula (1M) and the general formula (5M) From the total number of moles of the group selected from the substituent group A which the compound, the compound represented by the general formula (6M) and the compound represented by the general formula (7M) have, and the substituent group B What is necessary is just to adjust a ratio with the total number of moles of the selected group. Usually, the ratio of the total number of moles of the group selected from the substituent group B to the total number of moles of the group selected from the substituent group A is preferably 0.95 to 1.05, preferably 0.98 to 1.02 is more preferable, and 0.99 to 1.01 is still more preferable.

  In the method for producing a polymer compound according to the present invention, the charging ratio of the compound represented by the general formula (1M) with respect to all the compounds is preferably 0.1 mol% or more, and 20 mol% or less. It is preferable. Thereby, the high molecular compound whose ratio of the structural unit represented by the said General formula (1) with respect to the sum total of all the structural units is 0.1-20 mol% can be manufactured easily.

  In the method for producing a polymer compound according to the present invention, it is preferable to polymerize a monomer in the presence of a catalyst. As a catalyst, when polymerizing by a Suzuki coupling reaction, transition metals such as palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium, etc. Complexes, and complexes in which ligands such as triphenylphosphine, tri-tert-butylphosphine, and tricyclohexylphosphine are coordinated to these transition metal complexes.

  In the case of polymerization using a Ni (0) catalyst, the Ni (0) catalyst may be nickel [tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, [bis (1 , 4-cyclooctadiene)] nickel and other transition metal complexes, and these transition metal complexes include triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl, and the like. Examples thereof include a complex coordinated with a ligand.

  As the above-mentioned catalyst, a previously synthesized catalyst may be used, or a catalyst prepared in a reaction system may be used as it is. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.

  The amount of the catalyst used may be an effective amount as a catalyst. For example, it is usually 0.0001 to 300 mol% in terms of the number of moles of transition metal with respect to 100 mol% of all compounds in the polymerization reaction. Yes, preferably 0.001-50 mol%, more preferably 0.01-20 mol%.

  In polymerization by the Suzuki coupling reaction, it is preferable to use a base, and as the base, an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutyl fluoride, etc. Organic bases such as ammonium, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide can be mentioned.

  The usage-amount of a base is 50-2000 mol% normally with respect to a total of 100 mol% of all the compounds in a polymerization reaction, Preferably it is 100-1000 mol%.

  The polymerization reaction may be performed in the absence of a solvent or in the presence of a solvent, but is usually performed in the presence of an organic solvent. Here, examples of the organic solvent include toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. Since the molecular weight can be controlled, it is desirable to use a solvent subjected to deoxygenation treatment. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The amount of the organic solvent used is preferably such that the total concentration of all monomers in the polymerization reaction is 0.1 to 90% by weight, more preferably 1 to 50% by weight, The amount is more preferably 2 to 30% by weight.

  The reaction temperature of the polymerization reaction is preferably −100 to 200 ° C., more preferably −80 to 150 ° C., and still more preferably 0 to 120 ° C.

  The reaction time is usually 1 hour or longer, preferably 2 to 500 hours.

In the method for producing a polymer compound according to the present invention, when a compound having a group represented by —MgY ¹ as a group represented by Z ^{1 to} Z ⁸ is used, the polymerization reaction is preferably performed under dehydrating conditions. On the other hand, when the polymerization reaction is a Suzuki coupling reaction, the base used may be used as an aqueous solution, and water may be used as a solvent in addition to the organic solvent.

  In the polymerization reaction, a compound represented by the following formula (9) may be used as a chain terminator in order to avoid the polymerization active group remaining at the terminal of the polymer compound according to the present invention. Thereby, the high molecular compound whose terminal is an aryl group or a monovalent aromatic heterocyclic group can be obtained.

［式（９）中、Ａｒ⁷は、アリール基又は１価の芳香族複素環基を示す。Ｚ⁹は、置換基Ａ群及び置換基Ｂ群からなる群から選ばれる基を示す。］

[In the formula (9), Ar ⁷ represents an aryl group or a monovalent aromatic heterocyclic group. Z ⁹ represents a group selected from the group consisting of the substituent group A and the substituent group B. ]

In the formula (9), the aryl group and monovalent aromatic heterocyclic group in Ar ⁷ are the same as those described and exemplified as the above-mentioned aryl group and monovalent aromatic heterocyclic group, respectively.

  The post-treatment of the polymerization reaction can be performed by a known method. For example, the reaction solution after the polymerization reaction is added to a lower alcohol such as methanol, and the precipitated precipitate is filtered and dried.

  When the purity of the polymer compound according to the present invention is low, the polymer compound according to the present invention may be purified by a usual method such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, etc. When a compound is used for a light-emitting device, the purity affects the performance of the device such as light-emitting properties. Therefore, it is preferable to perform a purification treatment such as reprecipitation purification and fractionation by chromatography after condensation polymerization.

  As a method for producing the compound represented by the general formula (1M), a method for producing a compound represented by the following general formula (4M) will be described as an example.

［一般式（４）中、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹及びＥはそれぞれ独立に、前記と同じ意味を表す。Ｚ¹⁰及びＺ¹¹はそれぞれ独立に、前記置換基Ａ群及びＢ群からなる群から選ばれる基を示す。］

[In General Formula (4), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and E each independently represent the same meaning as described above. Z ¹⁰ and Z ¹¹ each independently represent a group selected from the group consisting of the substituent groups A and B. ]

  As a manufacturing method of the compound shown by the said General formula (4), following reaction formula (R1) or following reaction formula (R2) according to a well-known manufacturing method:

［式（Ｒ１）及び（Ｒ２）中、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹及びＥはそれぞれ独立に、前記と同じ意味を表す。Ｒ^15-1、Ｒ^15-2及びＲ^15-3はそれぞれ独立に、アルキル基、アリール基又は１価の芳香族複素環基を示す。Ｚ¹⁰及びＺ¹¹はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれる基を示す。］
で示される経路が挙げられる。

[In the formulas (R1) and (R2), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and E each independently represent the same meaning as described above. R ^15-1 , R ^15-2 and R ^15-3 each independently represent an alkyl group, an aryl group or a monovalent aromatic heterocyclic group. Z ¹⁰ and Z ¹¹ each independently represent a group selected from the group consisting of Substituent Group A and Substituent Group B. ]
The route shown by is mentioned.

The alkyl group, aryl group and monovalent aromatic heterocyclic group for R ^15-1 , R ^15-2 and R ^15-3 are the alkyl group, aryl group and monovalent aromatic group for R ¹ described above, respectively. This is the same as described and exemplified as the heterocyclic group.

Z ¹⁰ and Z ¹¹ are preferably a group selected from Substituent Group A, and more preferably a halogen atom, since the synthesis of a compound serving as a monomer is facilitated.

  In the step of “introduction of the substituent E”, preferred reactants include the following general formula (10):

［式（１０）中、Ｚ¹²は、置換基Ａ群から選ばれる基を示す。Ｅは、前記と同じ意味を表す。］
で示される化合物が挙げられる。

[In the formula (10), Z ¹² represents a group selected from the substituent group A. E represents the same meaning as described above. ]
The compound shown by these is mentioned.

In the general formula (10), Z ¹² is preferably a halogen atom because the compound is easy to handle.

  The substituent E can be introduced by converting the compound represented by the general formula (10) into a Grignard reagent or a lithium salt.

  Examples of the compound represented by the general formula (10) include the following formula described in Polycyclic Aromatic Compounds, 11 (1-4), 261-266; 1996:

で示されるブロモフルオランテン、Journal of Organic Chemistry, 62(3), 530-537; 1997に記載されている下記式：

Bromofluoranthene represented by the following formula described in Journal of Organic Chemistry, 62 (3), 530-537; 1997:

で示される３−ブロモジフェニルベンゾフルオランテン、下記反応式：

3-bromodiphenylbenzofluoranthene represented by the following reaction formula:

で製造できる９−又は１０−ブロモジフェニルベンゾフルオランテンが挙げられる。なお、式中の化合物は、置換基を有していてもよい。

9- or 10-bromodiphenylbenzofluoranthene which can be produced by In addition, the compound in a formula may have a substituent.

<Polymer composition>
The polymer composition according to the present invention contains the polymer compound according to the present invention and at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material.

  Examples of hole transport materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, polyaniline and derivatives thereof, polythiophene and Examples thereof include polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Examples thereof include compounds described in JP-A-379992 and JP-A-3-152184.

  The content of the hole transport material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound in the polymer composition.

  Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene And derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and the like. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Examples thereof include compounds described in JP-A-379992 and JP-A-3-152184.

  The content of the electron transport material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound in the polymer composition.

  Examples of the light emitting material include a low molecular fluorescent light emitting material and a phosphorescent light emitting material. Examples of light-emitting materials include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes and other dyes, and 8-hydroxyquinoline as a ligand. Metal complexes, metal complexes having 8-hydroxyquinoline derivatives as ligands, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, stilbene series, silicon-containing aromatics , Oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, acetylene and other low molecular weight fluorescent materials, iridium complexes, platinum complexes and other metal complexes, triple A term luminescent complex is mentioned. In addition, compounds described in JP-A-57-51781, JP-A-59-194393, and the like are also included.

  The content of the light emitting material is preferably 1 to 500 parts by weight, and more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound in the polymer composition. As the light emitting material, the light emitting material of the present invention is preferably used.

<Solution>
The polymer compound according to the present invention may be dissolved or dispersed in an organic solvent to form a solution. This solution or dispersion is called ink, liquid composition or the like. In addition to the polymer compound, the solution may contain at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material.

  Here, examples of the organic solvent include chloroform solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; toluene, Aromatic hydrocarbon solvents such as xylene, trimethylbenzene and mesitylene; aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane Solvents; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl Polyhydric alcohols and derivatives thereof such as ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol; methanol, ethanol, propanol, isopropanol, cyclo Examples include alcohol solvents such as hexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, an organic solvent having a structure containing a benzene ring, having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher is preferable because the viscosity and film formability are improved.

According to the said solution, the organic thin film containing the high molecular compound which concerns on this invention can be manufactured easily. Specifically, the organic thin film containing the polymer compound according to the present invention is obtained by applying the solution onto a substrate and distilling off the organic solvent by heating, decompression, or the like. The evaporation of the organic solvent can be changed depending on the organic solvent used. For example, the organic solvent can be distilled by heating at about 50 to 150 ° C. and reducing the pressure at about 10 ⁻³ Pa.

  For coating, spin coating method, casting method, micro gravure method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, screen printing A coating method such as a printing method, a flexographic printing method, an offset printing method, an inkjet printing method, or a nozzle coating method can be used.

  Although the suitable viscosity of the said solution changes also with printing methods, Preferably it is 0.5-500 mPa * s in 25 degreeC. Further, when the solution passes through a discharge device as in the ink jet printing method, the viscosity at 25 ° C. is preferably 0.5 to 20 mPa · s in order to prevent clogging and flight bending at the time of discharge.

<Organic thin film>
The organic thin film according to the present invention contains the polymer compound according to the present invention or the polymer composition according to the present invention. The organic thin film which concerns on this invention can be easily manufactured from the said solution as mentioned above.

  The organic thin film which concerns on this invention can be used conveniently as a light emitting layer in the light emitting element mentioned later. Moreover, the organic thin film which concerns on this invention can be used conveniently also for an organic-semiconductor element. Since the organic thin film which concerns on this invention contains the said high molecular compound, when it uses as a light emitting layer of a light emitting element, the light emission efficiency of the said light emitting element becomes very excellent.

<Organic semiconductor element>
By using the organic thin film according to the present invention, it is also possible to produce an organic semiconductor element. Examples of the organic semiconductor element include an organic thin film solar cell and a field effect organic transistor. Specifically, the organic thin film is formed on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and a source electrode and a drain electrode are formed using Au or the like, thereby forming a field effect organic transistor. be able to.

<Light emitting element>
The light emitting device according to the present invention includes the organic thin film. In a preferred embodiment, the light-emitting element according to the present invention includes an anode, a cathode, and a layer containing the polymer compound present between the anode and the cathode. Here, the layer containing the polymer compound is preferably a layer made of the organic thin film, and the layer preferably functions as a light emitting layer. Hereinafter, a case where the layer containing the polymer compound functions as a light emitting layer will be exemplified as a preferred embodiment.

Examples of the structure of the light emitting device according to the present invention include the following structures (a) to (d). Note that “/” indicates that the layers before and after that are stacked adjacent to each other (for example, “anode / light emitting layer” indicates that the anode and the light emitting layer are stacked adjacent to each other). .)
(A) Anode / light emitting layer / cathode (b) Anode / hole transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron transport layer / cathode (d) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode

  Note that the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. is there. The hole transport layer and the electron transport layer may be collectively referred to as a charge transport layer. The hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.

  Lamination and film formation of each layer can be performed using a solution containing the constituent components of each layer. For lamination and film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, inkjet printing, and nozzle coating can be used.

  The thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency are moderate values, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. .

  The hole transport layer preferably contains the hole transport material described above. The hole transport layer may be formed by any method, but when the hole transport material is a polymer compound, it is preferably formed from a solution containing the hole transport material. When the transport material is a low molecular compound, it is preferable to form a film from a mixed solution containing a polymer binder and a hole transport material. As a film forming method, a method similar to the above-described coating method can be used.

  The polymer binder is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

  The thickness of the hole transport layer may be selected so that the drive voltage and the light emission efficiency are appropriate. However, a thickness that does not generate pinholes is necessary, and if it is too thick, the drive voltage of the device increases. It is not preferable. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The electron transport layer preferably contains the electron transport material described above. The electron transport layer may be formed by any method. When the electron transport material is a polymer compound, a method of forming a film from a solution containing the electron transport material, A film forming method or the like is preferable. In addition, when the electron transport material is a low-molecular compound, a method of forming a film by vacuum deposition using a powder of the electron transport material, a method of forming a film from a solution containing the electron transport material, and melting the electron transport material Thus, a film forming method is preferable. Examples of a method for forming a film from a solution containing an electron transport material include the same methods as those described above. Moreover, the polymer binder may contain in the solution.

  The polymer binder is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. As the polymer binder, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The thickness of the electron transport layer may be selected so that the drive voltage and the light emission efficiency are appropriate values. However, a thickness that does not generate pinholes is necessary. Absent. Therefore, the thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Among the charge transport layers provided adjacent to the electrode, those having the function of improving the charge injection efficiency from the electrode and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers, Sometimes called an electron injection layer. In order to improve the adhesion with the electrode and the charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode. A thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. Note that the order and number of layers to be stacked, and the thickness of each layer may be selected in consideration of light emission efficiency and element lifetime.

Examples of the light emitting element provided with the charge injection layer include those having the following structures (e) to (p).
(E) Anode / charge injection layer / light emitting layer / cathode (f) Anode / light emitting layer / charge injection layer / cathode (g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode (h) anode / charge injection Layer / hole transport layer / light emitting layer / cathode (i) anode / hole transport layer / light emitting layer / charge injection layer / cathode (j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / Cathode (k) anode / charge injection layer / light emitting layer / charge transport layer / cathode (l) anode / light emitting layer / electron transport layer / charge injection layer / cathode (m) anode / charge injection layer / light emitting layer / electron transport layer / Charge injection layer / cathode (n) anode / charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode (o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode (P) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

  As the charge injection layer, (I) a layer containing a conductive polymer, (II) an anode material in the anode and a hole transport material in the hole transport layer provided between the anode and the hole transport layer; A layer containing a material having an ionization potential of an intermediate value of (III), provided between the cathode and the electron transport layer, and having an intermediate value between the cathode material in the cathode and the electron transport material in the electron transport layer Examples thereof include a layer containing a material having electron affinity.

When the charge injection layer is (I) a layer containing a conductive polymer, the electric conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm to 10 ³ S / cm, and the leakage current between the light emitting pixels for the smaller is more preferably ^{10 -5 S / cm~10 2 S /} cm, particularly preferably ^{10 -5 S / cm~10 1 S /} cm. In order to satisfy this range, the conductive polymer may be doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like. Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

  The thickness of the charge injection layer is preferably 1 to 100 nm, and more preferably 2 to 50 nm.

  The conductive polymer may be selected in relation to the electrode and the material of the adjacent layer. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its Examples thereof include conductive polymers such as derivatives, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polymers containing an aromatic amine structure in the main chain or side chain. Examples of the charge injection layer include a layer containing metal phthalocyanine (such as copper phthalocyanine) and carbon.

  The insulating layer has a function of facilitating charge injection. The thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the light emitting element provided with an insulating layer include those having the following structures (q) to (ab).
(Q) Anode / insulating layer / light emitting layer / cathode (r) anode / light emitting layer / insulating layer / cathode (s) anode / insulating layer / light emitting layer / insulating layer / cathode (t) anode / insulating layer / hole transport Layer / light emitting layer / cathode (u) anode / hole transport layer / light emitting layer / insulating layer / cathode (v) anode / insulating layer / hole transporting layer / light emitting layer / insulating layer / cathode (w) anode / insulating layer / Light emitting layer / electron transport layer / cathode (x) anode / light emitting layer / electron transport layer / insulating layer / cathode (y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode (z) anode / insulating Layer / hole transport layer / light emitting layer / electron transport layer / cathode (aa) anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode (ab) anode / insulating layer / hole transport layer / light emitting Layer / electron transport layer / insulating layer / cathode

  The light emitting device according to the present invention preferably includes a substrate adjacent to the anode or the cathode. The substrate is preferably a substrate whose shape and properties do not change when the electrode and each layer are formed, and includes a substrate of glass, plastic, polymer film, silicon or the like. In the case of an opaque substrate, the electrode on the side opposite to the electrode with which the substrate is in contact is preferably transparent or translucent.

  In the light-emitting device according to the present invention, it is usually preferable that at least one of the electrode composed of an anode and a cathode is transparent or translucent, and the anode is transparent or translucent.

  As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, it was produced using a conductive inorganic compound such as indium oxide, zinc oxide, tin oxide, composite oxide made of indium / tin / oxide (ITO), composite oxide made of indium / zinc / oxide, or the like. A film, NESA, gold, platinum, silver, copper, or the like is used. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode. In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. Good.

  Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  The thickness of the anode can be selected in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. .

  As a material for the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Europium, terbium, ytterbium and other metals, alloys containing two or more of the metals, one or more of the metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy containing one or more, graphite, a graphite intercalation compound, or the like is used.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used.

  The thickness of the cathode can be selected in consideration of electric conductivity and durability, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the light emitting layer or between the cathode and the electron transport layer. A protective layer for protecting the light emitting element may be attached. In order to use the light emitting element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, resins, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used, and a method of sealing the protective cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is used. Preferably used. If the space is maintained by using the spacer, the element can be easily prevented from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and further, moisture adsorbed in the manufacturing process can be obtained by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element.

  The light emitting device containing the polymer compound according to the present invention or the polymer composition according to the present invention includes a planar light source such as a curved light source or a planar light source (for example, illumination); a segment display device, a dot matrix display device It is useful for display devices such as a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display, etc.). The polymer compound according to the present invention is not only suitable as a material used for the production thereof, but also a dye for laser, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film, and an organic semiconductor thin film. It is also useful as a material for conductive thin films such as a light emitting thin film material that emits fluorescence, and a material for polymer field effect transistors.

  In order to obtain planar light emission using the light emitting element according to the present invention, the planar anode and cathode may be arranged so as to overlap each other. Further, in order to obtain pattern-like light emission, a method in which a mask provided with a pattern-like window is provided on the surface of the planar light-emitting element, either the anode or the cathode, or both electrodes in a pattern shape. There is a method of forming. A segment display device capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Furthermore, in order to obtain a dot matrix display device, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively or may be driven actively in combination with a TFT or the like. These display devices can be used in computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  The polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound were determined under the following measurement conditions using gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp).

[Measurement condition]
The polymer compound to be measured was dissolved in tetrahydrofuran (THF) to a concentration of about 0.05% by weight, and 10 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 2.0 ml / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

<Example 1>
{Synthesis of Compound 2}

To a 1 L four-necked eggplant flask, 23.2 g (100.2 mmol) of 4-bromophthalic anhydride was added and dissolved in THF (430 ml), and then the gas in the flask was replaced with nitrogen. After cooling the inside of the flask to −66 ° C., lithium tri (tert-butoxy) aluminum hydride solution (100.2 ml, 100.2 mmol, 1.0 M THF solution) was added dropwise. The reaction solution was stirred at −65 ° C. or lower for 2 hours, and water (100 ml) and dilute hydrochloric acid (400 ml) were added. The reaction solution was separated, and the aqueous layer was extracted twice with ethyl acetate (400 ml), and then the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to obtain 23.5 g of Compound 1 as a white solid. It was.
23.5 g of Compound 1 was placed in a 300 ml eggplant flask and dissolved in methanol (232 ml), and then the gas in the flask was replaced with nitrogen. The resulting solution was heated at 80 ° C. for 6 hours. Then, the solution obtained by allowing to cool was concentrated, and ethyl acetate (100 ml) and water (100 ml) were added to separate the solution. Further, the aqueous layer was extracted with ethyl acetate (100 ml). Next, the organic layer was washed with saturated brine (100 ml), and then the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to obtain 20.3 g of Compound 2 as a pale yellow oil.

{Synthesis of Compound 3}

  Compound 2 (16.2 g) was placed in a 1 L four-neck eggplant flask and dissolved in THF (267 ml), and then the gas in the flask was replaced with nitrogen. After cooling the resulting solution to 0 ° C., phenylmagnesium bromide (110.0 ml, 1.0 M THF solution) was added dropwise, and after 3 hours at this temperature, dilute hydrochloric acid (200 ml) was added dropwise. The reaction solution was separated, the aqueous layer was extracted twice with ethyl acetate (300 ml), and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to obtain 22.1 g of compound 3.

{Synthesis of Compound 5}

  Under an argon atmosphere, add 5-bromoacetylenylene (10 g), compound 4a (17.2 g), dichlorobis (triphenylphosphine) palladium (2.1 g), and 550 ml of toluene to a 1 L three-necked flask, and stir. Bubbling was performed with argon for 10 minutes. Thereto were added 2M aqueous potassium hydroxide solution (140 ml) and tetrabutylammonium bromide (0.6 mg), and the mixture was heated at 100 ° C. for 90 minutes and stirred. The reaction solution was returned to room temperature to stop the reaction. The aqueous layer was removed from the resulting solution, washed 3 times with 150 ml of water, and dehydrated with saturated brine. Thereto, sodium sulfate was added and dried, followed by filtration. The solution obtained after filtration was concentrated under reduced pressure, and then purified by silica gel column chromatography using hexane / chloroform as a developing solvent to obtain Compound 4 (13.5 g) as an orange powder.

Compound 3 (3.3 g), compound 4 (5.0 g) and 30 ml of xylene were charged and heated in an oil bath at 150 ° C. for 2 hours. Thereafter, 0.54 g of p-TsOH was added to the reaction solution at 110 ° C., and the mixture was heated and stirred at that temperature for 2 hours. Subsequently, after cooling to room temperature, toluene and water were added and stirred, liquid-separated and extracted, and the organic layer was obtained. The organic layer was washed with a 5% by weight aqueous sodium chloride solution and water, dried over anhydrous magnesium sulfate, and concentrated to dryness. The obtained product was separated and purified by silica gel column chromatography (hexane / chloroform) to obtain 1.8 g (yellow orange crystal) of compound 5 (mixture of compound 5a and compound 5b).
LC-MS (APCI, positive): [M + H] ⁺ 823

{Synthesis of Compound 6}

Compound 5 (3.2 g) was charged into a 100 ml glass container, the inside of the container was purged with argon, and 18 ml of THF was added dropwise. Then, it cooled to -70 degrees C or less with the dry ice-acetone bath, and 1.39 ml of 2.76M n-butyllithium / hexane solutions were dripped over about 10 minutes. Stirring was continued for 30 minutes, and then a mixture of 1.23 g of 2,7-dibromofluorenone and 18 ml of THF was added dropwise over 30 minutes. Along with the dropping, the reaction solution changed from dark reddish brown to red, and became a reddish orange transparent liquid after 1 hour of reaction. Thereafter, water was added dropwise to the reaction solution, followed by extraction with toluene. The obtained organic layer was washed twice with water and then dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated to dryness. The obtained product was separated and purified by silica gel column chromatography (hexane / toluene) to obtain 3.0 g (yellow orange powder) of compound 6 (mixture of compound 6a and compound 6b).
LC-MS (API-ES (ESI-KCl), positive): [M + K] ⁺ 1121

{Synthesis of Compound 7}

Compound 6 (2.8 g) was charged into a 200 ml glass container, the inside of the container was purged with argon, and 54 ml of cyclohexane was added dropwise. Thereafter, 1.25 ml of triethylsilane was added dropwise to the reaction solution at room temperature in about 10 minutes, and 3.9 ml of trifluoroacetic acid was added dropwise to the reaction solution over about 30 minutes. Two hours later, water was added dropwise thereto, followed by extraction using 300 ml of chloroform and 300 ml of toluene. The obtained organic layer was washed with 5% by weight aqueous solution of dipotassium hydrogenphosphate and water, dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated and dried to give compound 7 ( 2.8 g (light brown solid) of a mixture of compound 7a and compound 7b) was obtained.
LC-MS (APCI, negative) : [M-H] - 1065

{Synthesis of Compound 8}

Compound 7 (1.40 g) and 0.91 g of potassium carbonate were charged into a 50 ml glass container, and the inside of the container was purged with argon, and 1.01 g of n-octyl bromide, 21 ml of dimethyl sulfoxide (DMSO) and toluene 9. 6 ml was added dropwise. Thereafter, the container was heated to around 115 ° C. Before the temperature increase, the reaction solution was dark blue, but after 30 minutes of warming, the bluish color disappeared and a light brown reaction solution was obtained. Furthermore, after heating and stirring at 115-120 degreeC for 1 hour, it cooled to near room temperature. Thereafter, water was added dropwise to the reaction solution, extracted with toluene, washed with a 5 wt% aqueous sodium chloride solution and water, dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated to dryness. The obtained product was separated and purified by silica gel column chromatography to obtain 1.2 g (yellow solid) of Compound 8 (mixture of Compound 8a and Compound 8b). According to 1 H-NMR, the abundance ratio (molar ratio) between compound 8a and compound 8b in the mixture was approximately 50:50.
LC-MS (API-ES (ESI-KCl), positive): [M + K] ⁺ 1217

<Example 2>
{Synthesis of Compound 11}

  In a 500 ml four-necked flask under an argon atmosphere, 5-bromoacetylenylene (18 g), 2-naphthaleneboronic acid (14.7 g), tetrakistriphenylphosphine palladium (2.6 g), 260 ml of toluene, and 70 ml of ethanol. And stirred and bubbled with argon for 10 minutes. Thereto was added 82.6 g of a 25% by weight aqueous sodium carbonate solution, heated at 100 ° C. for 120 minutes, and stirred. The reaction solution was returned to room temperature to stop the reaction. The aqueous layer was removed from the resulting solution, washed 3 times with distilled water (150 ml), and dehydrated with saturated brine. After adding magnesium sulfate and activated carbon 2g there, it filtered. The solution obtained after filtration was concentrated under reduced pressure, and purified by silica gel column chromatography using hexane / ethyl acetate as a developing solvent to obtain Compound 10 (21.8 g) as an orange powder.

Compound 9 (2.2 g), compound 10 (1.0 g), and 10 ml of xylene were charged and heated in an oil bath at 150 ° C. for 2 hours. Thereafter, at 110 ° C., 0.11 g of p-TsOH was added thereto, and the mixture was heated and stirred at that temperature for 2 hours. Then, it cooled to room temperature, added toluene and water, stirred, and then separated and extracted to obtain an organic layer. This organic layer was washed with a 5 wt% aqueous sodium hydrogen carbonate solution and water, dried over anhydrous magnesium sulfate, and concentrated to dryness. The obtained product was separated and purified by silica gel column chromatography (hexane / chloroform) to obtain 1.6 g of compound 11 (mixture of compound 11a and compound 11b) (yellowish red oil).
LC-MS (APCI, positive): [M + H] ⁺ 946

{Synthesis of Compound 12}

Compound 11 (4.05 g) was charged into a 100 ml glass container, the inside of the container was purged with argon, and 23 ml of THF was added dropwise. Thereafter, the reaction solution was cooled to −70 ° C. or lower with a dry ice-acetone bath, and 1.6 ml of a 2.76 M n-butyllithium / hexane solution was added dropwise over about 10 minutes. Stirring was continued for 10 minutes, and then a mixture of 1.45 g of 2,7-dibromofluorenone and 18 ml of THF was added dropwise thereto over 10 minutes. After further stirring for 10 minutes, the temperature was raised to 0 ° C., water was added dropwise, and the mixture was extracted with toluene. The obtained organic layer was washed twice with water and then dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated to dryness. The obtained product was separated and purified by silica gel column chromatography (hexane / toluene) to obtain 3.6 g of compound 12 (mixture of compound 12a and compound 12b) (yellow oil).
LC-MS (APCI, positive): [M-OH] ⁺ 1187

{Synthesis of Compound 13}

  After charging Compound 12 (5.6 g) into a 200 ml glass container, the inside of the container was purged with argon, and 100 ml of cyclohexane was added dropwise. Thereafter, the reaction solution was cooled to 5 to 10 ° C., 2.3 ml of triethylsilane was dropped in about 2 minutes, and 10.7 ml of trifluoroacetic acid was dropped therein over about 10 minutes. After stirring for 2 hours, water was added dropwise thereto and extracted with hexane. The obtained organic layer was washed with 5% by weight aqueous solution of dipotassium hydrogenphosphate and water and then dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated to dryness and subjected to silica gel column chromatography. Separation and purification with (hexane / chloroform) gave 4.7 g (yellow oily product) of compound 13 (mixture of compound 13a and compound 13b).

{Synthesis of Compound 14}

Compound 13 (0.22 g) and 0.13 g of potassium carbonate were charged into a 50 ml glass container, and the inside of the container was purged with argon, and 0.14 g of n-octyl bromide, 3 ml of DMSO and 1.5 ml of toluene were added dropwise. Thereafter, the reaction solution was heated to around 115 ° C. Before the temperature increase, the reaction solution was dark blue, but after 30 minutes of warming, the bluish color disappeared and a light brown reaction solution was obtained. The reaction solution was heated and stirred at 115 to 120 ° C. for 1 hour, and then cooled to near room temperature. Thereafter, water was added dropwise thereto, extracted with toluene, washed with 5 wt% aqueous sodium hydrogen carbonate solution and water, dried over anhydrous magnesium sulfate, and the solution obtained after filtration was concentrated to dryness. . The obtained product was separated and purified by silica gel column chromatography (hexane / chloroform) to obtain 0.16 g (yellow solid) of Compound 14 (mixture of Compound 14a and Compound 14b). According to 1 H-NMR, the abundance ratio (molar ratio) between compound 14a and compound 14b in the mixture was approximately 50:50.
LC-MS (APCI, positive): [M] ⁺ 1302

<Example 3>
{Synthesis of polymer compound A}
Under argon atmosphere, the following formula:

で表される化合物（０．１６３ｇ、０．２０ｍｍｏｌ）と、下記式：

And a compound represented by formula (0.163 g, 0.20 mmol):

で表される化合物（０．３６０ｇ、０．５６ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (0.360 g, 0.56 mmol)

で表される化合物（１．０６４ｇ、１．４４ｍｍｏｌ）と、下記式：

And a compound represented by formula (1.064 g, 1.44 mmol):

で表される化合物（１．０３１ｇ、１．６０ｍｍｏｌ）と、化合物８（０．２３６ｇ、０．２０ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（１．４ｍｇ）と、トルエン（５０ｍｌ）とを混合し、１０５℃に加熱した。得られた溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍｌ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（２４．４ｍｇ）及びトルエン（５ｍｌ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水（２６ｍｌ）で２回、３重量％酢酸水溶液（２６ｍｌ）で２回、水（２６ｍｌ）で２回洗浄し、得られた溶液をメタノール（４００ｍｌ）に滴下、ろ取することで沈殿物を得た。該沈殿物をトルエン（８０ｍｌ）に溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４００ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、下記式（Ｋ−１）（２種の構成単位の存在比（モル比）は、およそ５０：５０）で表される構成単位と、下記式（Ｋ−２）で表される構成単位と、下記式（Ｋ−３）で表される構成単位と、下記式（Ｋ−４）で表される構成単位とを、５：１４：５：７６のモル比で有する重合体（以下、「高分子化合物Ａ」と言う。）を１．４７ｇ得た。
高分子化合物Ａのポリスチレン換算数平均分子量は８．５×１０⁴であり、ポリスチレン換算重量平均分子量は２．３９×１０⁵であった。

A compound represented by formula (1.031 g, 1.60 mmol), compound 8 (0.236 g, 0.20 mmol), dichlorobis (triphenylphosphine) palladium (1.4 mg), and toluene (50 ml) are mixed. And heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 ml) was added dropwise to the resulting solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 ml) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water (26 ml), twice with a 3% by weight aqueous acetic acid solution (26 ml) and twice with water (26 ml), and the resulting solution was added dropwise to methanol (400 ml). A precipitate was obtained. The precipitate was dissolved in toluene (80 ml) and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (400 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain the following formula (K-1) (abundance ratio of two structural units (moles). Ratio) is a structural unit represented by about 50:50), a structural unit represented by the following formula (K-2), a structural unit represented by the following formula (K-3), and the following formula ( 1.47 g of a polymer (hereinafter referred to as “polymer compound A”) having a structural unit represented by K-4) at a molar ratio of 5: 14: 5: 76 was obtained.
The polymer compound A had a polystyrene equivalent number average molecular weight of 8.5 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.39 × 10 ⁵ .

<Example 4>
{Synthesis of polymer compound B}
Under argon atmosphere, the following formula:

で表される化合物（０．１６３ｇ、０．２０ｍｍｏｌ）と、下記式：

And a compound represented by formula (0.163 g, 0.20 mmol):

で表される化合物（０．３６０ｇ、０．５６ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (0.360 g, 0.56 mmol)

で表される化合物（１．１０４ｇ、１．４４ｍｍｏｌ）と、下記式：

And a compound represented by formula (1.104 g, 1.44 mmol):

で表される化合物（１．０３１ｇ、１．６０ｍｍｏｌ）と、化合物１４（０．２６０ｇ、０．２０ｍｍｏｌ）と、酢酸パラジウム（０．６７ｍｇ）と、トリス（ｏ−メトキシフェニル）ホスフィン（４．２３ｍｇ）と、１−ヘキセン（１０．１ｍｇ、０．１２ｍｍｏｌ）と、トルエン（５０ｍｌ）とを混合し、１０５℃に加熱した。得られた溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍｌ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（２４．４ｍｇ）及びトルエン（５ｍｌ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水（２６ｍｌ）で２回、３重量％酢酸水溶液（２６ｍｌ）で２回、水（２６ｍｌ）で２回洗浄し、得られた溶液をメタノール（４００ｍｌ）に滴下、ろ取することで沈殿物を得た。この沈殿物をトルエン（８０ｍｌ）に溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４００ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、下記式（Ｋ−５）（２種の構成単位の存在比（モル比）は、およそ５０：５０）で表される構成単位と、前記式（Ｋ−２）で表される構成単位と、前記式（Ｋ−３）で表される構成単位と、下記式（Ｋ−６）で表される構成単位と、下記式（Ｋ−７）で表される構成単位とを、５：１４：５：３６：４０のモル比で有する重合体（以下、「高分子化合物Ｂ」と言う。）を１．３７ｇ得た。
高分子化合物Ｂのポリスチレン換算数平均分子量は１．０２×１０⁵であり、ポリスチレン換算重量平均分子量は３．０２×１０⁵であった。

(1.031 g, 1.60 mmol), Compound 14 (0.260 g, 0.20 mmol), palladium acetate (0.67 mg), and tris (o-methoxyphenyl) phosphine (4.23 mg) ), 1-hexene (10.1 mg, 0.12 mmol) and toluene (50 ml) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 ml) was added dropwise to the resulting solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 ml) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water (26 ml), twice with a 3% by weight aqueous acetic acid solution (26 ml) and twice with water (26 ml), and the resulting solution was added dropwise to methanol (400 ml). A precipitate was obtained. This precipitate was dissolved in toluene (80 ml) and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (400 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to give the following formula (K-5) (abundance ratio of two structural units (moles). Ratio) is about 50:50), the structural unit represented by the formula (K-2), the structural unit represented by the formula (K-3), and the following formula ( A polymer (hereinafter referred to as “polymer”) having a structural unit represented by K-6) and a structural unit represented by the following formula (K-7) in a molar ratio of 5: 14: 5: 36: 40. 1.37 g of compound B ").
The polymer compound B had a polystyrene equivalent number average molecular weight of 1.02 × 10 ⁵ and a polystyrene equivalent weight average molecular weight of 3.02 × 10 ⁵ .

<Example 5>
{Synthesis of polymer compound C}
Under argon atmosphere, the following formula:

で表される化合物（０．３６０ｇ、０．５６ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (0.360 g, 0.56 mmol)

で表される化合物（１．１０４ｇ、１．４４ｍｍｏｌ）と、下記式：

And a compound represented by formula (1.104 g, 1.44 mmol):

で表される化合物（１．０３１ｇ、１．６０ｍｍｏｌ）と、化合物１４（０．５２１ｇ、０．４０ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（１．４ｍｇ）と、トルエン（５０ｍｌ）とを混合し、１０５℃に加熱した。得られた溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍｌ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（２４．４ｍｇ）及びトルエン（５ｍｌ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水（２６ｍｌ）で２回、３重量％酢酸水溶液（２６ｍｌ）で２回、水（２６ｍｌ）で２回洗浄し、得られた溶液をメタノール（４００ｍｌ）に滴下、ろ取することで沈殿物を得た。該沈殿物をトルエン（８０ｍｌ）に溶解させ、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４００ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、前記式（Ｋ−５）（２種の構成単位の存在比（モル比）は、およそ５０：５０）で表される構成単位と、前記式（Ｋ−２）で表される構成単位と、前記式（Ｋ−６）で表される構成単位と、前記式（Ｋ−７）で表される構成単位を１０：１４：３６：４０のモル比で有する重合体（以下、「高分子化合物Ｃ」と言う。）を１．３２ｇ得た。
高分子化合物Ｃのポリスチレン換算数平均分子量は７．８×１０⁴であり、ポリスチレン換算重量平均分子量は２．５５×１０⁵であった。

A compound represented by formula (1.031 g, 1.60 mmol), compound 14 (0.521 g, 0.40 mmol), dichlorobis (triphenylphosphine) palladium (1.4 mg), and toluene (50 ml) are mixed. And heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 ml) was added dropwise to the resulting solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 ml) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water (26 ml), twice with a 3% by weight aqueous acetic acid solution (26 ml) and twice with water (26 ml), and the resulting solution was added dropwise to methanol (400 ml). A precipitate was obtained. The precipitate was dissolved in toluene (80 ml) and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (400 ml) and stirred, and then the resulting precipitate was collected by filtration and dried to obtain the above-mentioned formula (K-5) (abundance ratio of two structural units (moles). Ratio) is a structural unit represented by approximately 50:50), a structural unit represented by the formula (K-2), a structural unit represented by the formula (K-6), and the formula ( 1.32 g of a polymer having a structural unit represented by K-7) at a molar ratio of 10: 14: 36: 40 (hereinafter referred to as “polymer compound C”) was obtained.
The polymer compound C had a polystyrene equivalent number average molecular weight of 7.8 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.55 × 10 ⁵ .

<Synthesis Example 1>
{Synthesis of polymer compound E}
In an inert atmosphere, the following formula:

で表される化合物（３．８６３ｇ、７．２８３ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (3.863 g, 7.283 mmol)

で表される化合物（３．１７７ｇ、６．９１９ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (3.177 g, 6.919 mmol)

で表される化合物（１５６．３ｍｇ、０．３６４ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（４．９ｍｇ）と、第四級アンモニウムクロライドの０．７４Ｍトルエン溶液（Ａｌｄｒｉｃｈ社製、商品名：Ａｌｉｑｕａｔ３３６、３．１ｍｌ）と、トルエン（５０ｍｌ）とを混合し、１０５℃に加熱した。得られた溶液に炭酸ナトリウム水溶液（２．０Ｍ、１４ｍｌ）を滴下し、１６．５時間還流させた。反応後、そこに、フェニルホウ酸（０．５ｇ）及びトルエン（１４０ｍｌ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチオカルバミン酸ナトリウム０．７５ｇ及び水５０ｍｌを添加した。反応物を油浴（８５℃）中、１６時間撹拌した。反応溶液から、水層を除去し、得られた有機層を水（１００ｍｌ）で３回洗浄し、次いでシリカゲル及び塩基性アルミナのカラムに通した。次いで、得られた溶液をメタノールに沈殿させ、得られた固体を、再度、トルエンに溶解させた後にメタノールに沈殿させ、得られた高分子化合物を６０℃で真空乾燥させ、下記式（Ｋ−９）で表される構成単位と、下記式（Ｋ−１０）で表される構成単位と、前記式（Ｋ−２）で表される構成単位とを、４７．５：２．５：５０のモル比で有する重合体（以下、「高分子化合物Ｅ」と言う。）を４．２ｇ得た。
高分子化合物Ｅのポリスチレン換算数平均分子量は４．４×１０⁴であり、ポリスチレン換算重量平均分子量は１．２４×１０⁵であった。

(156.3 mg, 0.364 mmol), dichlorobis (triphenylphosphine) palladium (4.9 mg), and a 0.74 M toluene solution of quaternary ammonium chloride (manufactured by Aldrich, trade name: Aliquat 336) 3.1 ml) and toluene (50 ml) were mixed and heated to 105 ° C. A sodium carbonate aqueous solution (2.0 M, 14 ml) was added dropwise to the resulting solution, and the mixture was refluxed for 16.5 hours. After the reaction, phenylboric acid (0.5 g) and toluene (140 ml) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, 0.75 g of sodium diethyldithiocarbamate and 50 ml of water were added thereto. The reaction was stirred in an oil bath (85 ° C.) for 16 hours. The aqueous layer was removed from the reaction solution, and the resulting organic layer was washed three times with water (100 ml) and then passed through a column of silica gel and basic alumina. Subsequently, the obtained solution was precipitated in methanol, and the obtained solid was again dissolved in toluene and then precipitated in methanol. The obtained polymer compound was vacuum-dried at 60 ° C., and the following formula (K− The structural unit represented by 9), the structural unit represented by the following formula (K-10), and the structural unit represented by the formula (K-2) are 47.5: 2.5: 50. 4.2 g of a polymer having a molar ratio (hereinafter referred to as “polymer compound E”) was obtained.
The polymer compound E had a polystyrene-equivalent number average molecular weight of 4.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.24 × 10 ⁵ .

<Example 6>
{Production and evaluation of organic EL element A}
An ethylene glycol monobutyl ether / water (3/2 (volume ratio)) solution of polythiophenesulfonic acid (Sigma Aldrich, trade name: Plexcore OC 1200) is applied to a glass substrate with an ITO film having a thickness of 45 nm formed by sputtering. The film was formed by spin coating to a thickness of 50 nm, and dried on a hot plate at 170 ° C. for 15 minutes.
Next, the polymer compound E was spin-coated in a 0.7% by weight xylene solution to form a film having a thickness of about 20 nm. Then, it heated at 180 degreeC for 60 minute (s) on the hotplate, and the film | membrane A was obtained.
Thereafter, the polymer compound A was dissolved in a xylene solvent at a concentration of 1.3% by weight, and was further formed on the film A by spin coating at a rotational speed of 2000 rpm to obtain a film B. The thickness of the film B was about 60 nm. After the film B was dried at 130 ° C. for 10 minutes in a nitrogen gas atmosphere, sodium fluoride was vacuum-deposited at about 3 nm as a cathode, and then aluminum was vacuum-deposited at about 80 nm to produce an organic EL device A. In vacuum deposition, metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
When voltage was applied to the organic EL device A, EL light emission having a peak at 470 nm derived from the polymer compound A was obtained from this device. The organic EL element A started to emit light at 2.9 V, showed light emission of 1000 cd / m ² at 5.2 V, and the maximum light emission efficiency was 6.9 cd / A.

<Example 7>
{Production and evaluation of organic EL element B}
In Example 6, instead of dissolving the polymer compound A in a xylene solvent at a concentration of 1.3% by weight, the polymer compound B was dissolved in a xylene solvent at a concentration of 1.2% by weight, and spin An organic EL element B was produced in the same manner as in Example 6 except that the rotation speed of the coat was changed from 2000 rpm to 1600 rpm. When voltage was applied to the organic EL element B, EL light emission having a peak at 475 nm derived from the polymer compound B was obtained. The organic EL element B started to emit light at 2.7 V, showed light emission of 1000 cd / m ^{2 at} 4.4 V, and the maximum light emission efficiency was 7.6 cd / A.

<Example 8>
{Production and evaluation of organic EL element C}
In Example 6, instead of dissolving the polymer compound A in the xylene solvent at a concentration of 1.3% by weight, the polymer compound C was dissolved in the xylene solvent at a concentration of 1.2% by weight, and spin An organic EL device C was produced in the same manner as in Example 6 except that the rotation speed of the coat was changed from 2000 rpm to 1500 rpm. When voltage was applied to the organic EL element C, EL light emission having a peak at 480 nm derived from the polymer compound C was obtained. The organic EL element C started to emit light at 2.8 V, showed light emission of 1000 cd / m ^{2 at} 4.6 V, and the maximum light emission efficiency was 7.0 cd / A.

<Comparative Example 1>
{Synthesis of polymer compound D}
Under argon atmosphere, the following formula:

で表される化合物（１．１９３ｇ、２．２５ｍｍｏｌ）と、下記式：

And a compound represented by formula (1.193 g, 2.25 mmol):

で表される化合物（０．９８７ｇ、１．８０ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (0.987 g, 1.80 mmol)

で表される化合物（０．３９０ｇ、０．４５０ｍｍｏｌ）と、トリオクチルメチルアンモニウムクロライド（Ａｌｄｒｉｃｈ社製、商品名：Ａｌｉｑｕａｔ３３６）（０．２９ｇ、０．７２ｍｍｏｌ）とをアルゴンガス雰囲気下、トルエン（１７．５ｍｌ）に溶解させた。溶液中へアルゴンガスをバブリングした後、８０℃まで昇温し、ジクロロビストリフェニルホスフィンパラジウム（１．６ｍｇ、２．３μmol）のトルエン懸濁液（５ｍｌ）を仕込み、更に２０重量％テトラエチルアンモニウム水酸化物水溶液（７．３ｍｌ、１０．４ｍｍｏｌ）を加え、還流下で７時間反応させた。冷却した後に、そこに、フェニルホウ酸 （０．２７ｇ、２．２５ｍｍｏｌ）をトルエン３ｍｌに懸濁させた溶液を加え、還流下で２時間反応させた。反応溶液にトルエン（２２ｍｌ）を加え希釈した後に、水層を除去し、９重量％Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム水溶液（１４ｍｌ）を加え、９０℃で２時間攪拌した。次いで、得られた有機層をイオン交換水（３０ｍｌ）で２回、３重量％酢酸水溶液（３０ｍｌ）で２回、イオン交換水（３０ｍｌ）で２回順次洗浄した後、メタノール（３５０ｍｌ）へ滴下し、３０分攪拌したところ、析出物が得られた。この析出物を吸引ろ過でろ取し、メタノールで洗浄した後、ろ取し、減圧して乾燥させることで沈殿物を得た。この沈殿物をアルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４００ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、下記式（Ｋ−８）で表される構成単位と、前記式（Ｋ−２）で表される構成単位を１０：９０のモル比で有する重合体（以下、「高分子化合物Ｄ」と言う。）を１．６５ｇ得た。
高分子化合物Ｄのポリスチレン換算の数平均分子量は２．８×１０⁴であり、ポリスチレン換算の重量平均分子量は６．１×１０⁴であった。

The compound represented by the formula (0.390 g, 0.450 mmol) and trioctylmethylammonium chloride (manufactured by Aldrich, trade name: Aliquat 336) (0.29 g, 0.72 mmol) in toluene (17 .5 ml). After bubbling argon gas into the solution, the temperature was raised to 80 ° C., charged with a toluene suspension (5 ml) of dichlorobistriphenylphosphine palladium (1.6 mg, 2.3 μmol), and further 20 wt% tetraethylammonium hydroxide. Aqueous solution (7.3 ml, 10.4 mmol) was added and reacted under reflux for 7 hours. After cooling, a solution in which phenylboric acid (0.27 g, 2.25 mmol) was suspended in 3 ml of toluene was added thereto, and the mixture was reacted for 2 hours under reflux. Toluene (22 ml) was added to the reaction solution for dilution, and then the aqueous layer was removed. A 9 wt% sodium N, N-diethyldithiocarbamate aqueous solution (14 ml) was added, and the mixture was stirred at 90 ° C. for 2 hours. Next, the obtained organic layer was washed successively with ion-exchanged water (30 ml) twice, 3% by weight acetic acid aqueous solution (30 ml) and twice with ion-exchanged water (30 ml), and then dropped into methanol (350 ml). Then, after stirring for 30 minutes, a precipitate was obtained. The precipitate was collected by suction filtration, washed with methanol, collected by filtration, and dried under reduced pressure to obtain a precipitate. The precipitate was purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (400 ml) and stirred, and then the resulting precipitate was collected by filtration and dried, whereby the structural unit represented by the following formula (K-8) and the above formula ( 1.65 g of a polymer having a structural unit represented by K-2) at a molar ratio of 10:90 (hereinafter referred to as “polymer compound D”) was obtained.
The polymer compound D had a polystyrene-equivalent number average molecular weight of 2.8 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 6.1 × 10 ⁴ .

{Production and evaluation of organic EL element D}
In Example 6, instead of dissolving the polymer compound A in the xylene solvent at a concentration of 1.3% by weight, the polymer compound D was dissolved in the xylene solvent at a concentration of 1.5% by weight, and spin An organic EL element D was produced in the same manner as in Example 6 except that the rotation speed of the coat was changed from 2000 rpm to 1400 rpm. When voltage was applied to the organic EL element D, EL light emission having a peak at 450 nm derived from the polymer compound D was obtained. The organic EL element D started to emit light at 3.3 V, showed light emission of 1000 cd / m ^{2 at} 5.3 V, and the maximum light emission efficiency was 2.0 cd / A.

<Comparative example 2>
{Synthesis of polymer compound F}
Under argon atmosphere, the following formula:

で表される化合物（１．１９３ｇ、２．２５ｍｍｏｌ）と、下記式：

And a compound represented by formula (1.193 g, 2.25 mmol):

で表される化合物（０．９８７ｇ、１．８０ｍｍｏｌ）と、下記式：

And a compound represented by the following formula: (0.987 g, 1.80 mmol)

で表される化合物（０．３４０ｇ、０．４５０ｍｍｏｌ）と、トリオクチルメチルアンモニウムクロライド（Ａｌｄｒｉｃｈ社製、商品名：Ａｌｉｑｕａｔ３３６）（０．２９ｇ、０．７２ｍｍｏｌ）とを、トルエン（１７．５ｍｌ）に溶解させた。溶液中へアルゴンガスをバブリングした後、８０℃まで昇温し、ジクロロビストリフェニルホスフィンパラジウム（１．６ｍｇ、２．３μｍｏｌ）のトルエン懸濁液（５ｍｌ）を滴下し、更に２０重量％テトラエチルアンモニウム水酸化物水溶液（７．３ｍｌ、１０．４ｍｍｏｌ）を加え、還流下で７時間反応させた。反応溶液を冷却した後に、そこに、フェニルホウ酸（０．２７ｇ、２．２５ｍｍｏｌ）をトルエン３ｍｌに懸濁させた溶液を加え、還流下で２時間反応させた。反応溶液にトルエン（２２ｍｌ）を加え希釈した後に、水層を除去し、９重量％Ｎ，Ｎ−ジエチルジチオカルバミド酸ナトリウム水溶液（１４ｍｌ）を加え、９０℃で２時間攪拌した。次いで、得られた有機層をイオン交換水（３０ｍｌ）で２回、３重量％酢酸水溶液（３０ｍｌ）で２回、イオン交換水（３０ｍｌ）で２回順次洗浄した後、メタノール（３５０ｍｌ）へ滴下し、３０分攪拌したところ、析出物が得られた。この析出物を吸引ろ過でろ取し、メタノールで洗浄した後、ろ取し、減圧して乾燥させることで沈殿物を得た。この沈殿物を、アルミナカラム、シリカゲルカラムを順番に通すことにより精製した。得られた溶液をメタノール（４００ｍｌ）に滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、下記式（Ｋ−１１）で表される構成単位と、前記式（Ｋ−２）で表される構成単位を１０：９０のモル比で有する重合体（以下、「高分子化合物Ｆ」と言う。）を１．６ｇ得た。
高分子化合物Ｆのポリスチレン換算の数平均分子量は１．７×１０⁴であり、ポリスチレン換算の重量平均分子量は３．２×１０⁴であった。

And a compound represented by the formula (0.340 g, 0.450 mmol) and trioctylmethylammonium chloride (manufactured by Aldrich, trade name: Aliquat 336) (0.29 g, 0.72 mmol) in toluene (17.5 ml) Dissolved. After bubbling argon gas into the solution, the temperature was raised to 80 ° C., a toluene suspension (5 ml) of dichlorobistriphenylphosphine palladium (1.6 mg, 2.3 μmol) was added dropwise, and further 20 wt% tetraethylammonium water. An aqueous oxide solution (7.3 ml, 10.4 mmol) was added and reacted under reflux for 7 hours. After cooling the reaction solution, a solution obtained by suspending phenylboric acid (0.27 g, 2.25 mmol) in 3 ml of toluene was added thereto and reacted for 2 hours under reflux. Toluene (22 ml) was added to the reaction solution for dilution, and then the aqueous layer was removed. A 9 wt% sodium N, N-diethyldithiocarbamate aqueous solution (14 ml) was added, and the mixture was stirred at 90 ° C. for 2 hours. Next, the obtained organic layer was washed successively with ion-exchanged water (30 ml) twice, 3% by weight acetic acid aqueous solution (30 ml) and twice with ion-exchanged water (30 ml), and then dropped into methanol (350 ml) Then, after stirring for 30 minutes, a precipitate was obtained. The precipitate was collected by suction filtration, washed with methanol, collected by filtration, and dried under reduced pressure to obtain a precipitate. This precipitate was purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol (400 ml) and stirred, and then the resulting precipitate was collected by filtration and dried, whereby the structural unit represented by the following formula (K-11) and the above formula ( 1.6 g of a polymer (hereinafter referred to as “polymer compound F”) having a structural unit represented by K-2) at a molar ratio of 10:90 was obtained.
The polymer compound F had a polystyrene-equivalent number average molecular weight of 1.7 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 3.2 × 10 ⁴ .

{Production and evaluation of organic EL element F}
In Example 6, instead of dissolving the polymer compound A in the xylene solvent at a concentration of 1.3% by weight, the polymer compound F was dissolved in the xylene solvent at a concentration of 2.1% by weight, and spin An organic EL element F was produced in the same manner as in Example 6 except that the rotation speed of the coat was changed from 2000 rpm to 3810 rpm. When voltage was applied to the organic EL element F, EL emission having a peak at 495 nm derived from the polymer compound F was obtained. The organic EL element F started to emit light at 2.9 V, showed light emission of 1000 cd / m ^{2 at} 4.3 V, and the maximum light emission efficiency was 4.5 cd / A.

Claims (20)

The high molecular compound containing the structural unit represented by following General formula (1).

[In General Formula (1), Ar ¹ represents an unsubstituted or substituted aromatic hydrocarbon group or an unsubstituted or substituted aromatic heterocyclic group. E represents the following general formula (2):

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A, which may have a substituent, and R ^A is an alkyl group, an aryl group, or , a monovalent aromatic heterocyclic group, when these groups which may have a substituent group .R ^a there are multiple, they may be different even in the same .R ¹ And R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁹ , R ⁹ and R ¹⁰ , R ¹ and R ⁸ and R ¹⁰ and R ⁸ may combine with each other to form a ring.)
The group formed by removing one hydrogen atom in the compound represented by this. aa is an integer of 1 or more. ] The polymer compound according to claim 1, wherein E is a group formed by removing one hydrogen atom from a compound represented by the following general formula (3).

[In general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic group. A heterocyclic group or a group represented by —O—R ^A is shown, and these groups may have a substituent. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ¹ and R ⁸ are bonded to each other, A ring may be formed. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or a group represented by —O—R ^A , This group may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ] The polymer compound according to claim 1 or 2, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (4).

[In General Formula (4), R ¹⁵ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , or a group represented by E. And these groups may have a substituent. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently represented by a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or —O—R ^A. These groups may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. R ¹⁷ and R ¹⁸ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a ring. E has the same meaning as described above. ] The high molecular compound as described in any one of Claims 1-3 containing the 1st structural unit represented by the said General formula (1), and the 2nd structural unit represented by the following general formula (5).

[In General Formula (5), R ²² and R ²³ each independently represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. . ] A first structural unit represented by the general formula (1);
A second structural unit represented by the general formula (5);
Any one of Claims 1-4 containing at least 1 type of structural unit chosen from the group which consists of the 3rd structural unit represented by following General formula (6), and the 4th structural unit represented by following General formula (7). The polymer compound according to claim 1.

[In General Formula (6), Ar ² is an arylene group, a divalent aromatic heterocyclic group, or two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group. A linked divalent group is shown. Ar ² represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O) —R ^A. At least selected from the group consisting of: a group represented by —C (═O) —O—R ^A , a group represented by —N (R ^A ) ₂ , a cyano group, and a fluorine atom. It may have one substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ]

[In the general formula (7), Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group. And a divalent group in which two or more identical or different groups selected from the group consisting of divalent aromatic heterocyclic groups are linked. Ar ³ and Ar ⁴ , Ar ³ and Ar ⁶ , and Ar ⁴ and Ar ⁵ are each a single bond, or —O—, —S—, —C (═O) —, —C (= O) -O -, - N ( R a) -, - C (= O) -N (R a) - or -C (R ^a) ₂ - a bond to via a group represented by the ring It may be formed. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group, and these groups may have a substituent. Good. a represents an integer of 0 to 3, and b represents 0 or 1. ]   A first structural unit represented by the general formula (1), a second structural unit represented by the general formula (5), and a fourth structural unit represented by the general formula (7). Item 6. The polymer compound according to Item 4 or 5. The said E is a group formed by removing one hydrogen atom from the group or atom represented by R ⁹ or R ¹⁰ in the general formula (2). The polymer compound described. The E is a group obtained by removing one hydrogen atom from the group or atom represented by R ³ or R ⁴ in the general formula (2) or (3). The polymer compound according to item. The E is a group obtained by removing one hydrogen atom from a group or atom represented by R ¹² or R ¹³ in the general formula (3). High molecular compound.   The polymer compound according to claim 1, which is a conjugated polymer compound.   The content of the first structural unit is 0.1 to 50 mol% with respect to the total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. The polymer compound according to any one of claims 4 to 10.   The total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit is 80 to 100% by weight with respect to the total amount of the polymer compound. The high molecular compound as described in any one of -11. The compound represented by the following general formula (1M).

[In General Formula (1M), Ar ¹ represents an unsubstituted or substituted aromatic hydrocarbon group or an unsubstituted or substituted aromatic heterocyclic group. E represents the following general formula (2):

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A, which may have a substituent, and R ^A is an alkyl group, an aryl group, or , a monovalent aromatic heterocyclic group, when these groups which may have a substituent group .R ^a there are multiple, they may be different even in the same .R ¹ And R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁹ , R ⁹ and R ¹⁰ , R ¹ and R ⁸ and R ¹⁰ and R ⁸ may combine with each other to form a ring.)
The group formed by removing one hydrogen atom in the compound represented by this. Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. aa is an integer of 1 or more. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ²⁷ (R ²⁷ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)
<Substituent group B>
—B (OR ²⁸ ) ₂ (R ²⁸ represents a hydrogen atom or an alkyl group. Two R ^{28 s} may be the same or different and may be bonded to each other to form a ring. . good), a group represented _{^{by, -BF 4 -. Q 1 (}} Q 1 is lithium, sodium, potassium, monovalent shows a cation) a group represented by the rubidium or cesium, -MgY ¹ (Y ¹ represents a chlorine atom, a bromine atom or an iodine atom), a group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn ( R ²⁹ ) ₃ (R ²⁹ represents a hydrogen atom or an alkyl group. The three R ^{29 s} may be the same or different and may combine with each other to form a ring.) A group represented by It is a manufacturing method of the high molecular compound as described in any one of Claims 4-12, Comprising: The compound represented by the following general formula (1M) and the compound shown by the following general formula (5M) are superposed | polymerized. The manufacturing method of a high molecular compound including a process.

[In General Formula (1M), Ar ¹ represents an unsubstituted or substituted aromatic hydrocarbon group or an unsubstituted or substituted aromatic heterocyclic group. E represents the following general formula (2):

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A, which may have a substituent, and R ^A is an alkyl group, an aryl group, or , a monovalent aromatic heterocyclic group, when these groups which may have a substituent group .R ^a there are multiple, they may be different even in the same .R ¹ And R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁹ , R ⁹ and R ¹⁰ , R ¹ and R ⁸ and R ¹⁰ and R ⁸ may combine with each other to form a ring.)
The group formed by removing one hydrogen atom in the compound represented by this. Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. aa is an integer of 1 or more. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ²⁷ (R ²⁷ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)
<Substituent group B>
—B (OR ²⁸ ) ₂ (R ²⁸ represents a hydrogen atom or an alkyl group. Two R ^{28 s} may be the same or different and may be bonded to each other to form a ring. A group represented by -BF ₄ Q ¹ (Q ¹ represents a monovalent cation of lithium, sodium, potassium, rubidium or cesium), -MgY ¹ (Y ¹ Represents a chlorine atom, a bromine atom or an iodine atom), a group represented by -ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), -Sn (R ²⁹ ) ₃ (R ²⁹ represents a hydrogen atom or an alkyl group. The three R ^{29 s} may be the same or different and may be bonded to each other to form a ring). The group represented.

[In General Formula (5M), R ²² and R ²³ each independently represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. . Z ³ and Z ⁴ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]   A polymer composition comprising the polymer compound according to any one of claims 1 to 12 and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.   The solution containing the high molecular compound and solvent as described in any one of Claims 1-12.   An organic thin film containing the polymer compound according to any one of claims 1 to 12 or the polymer composition according to claim 15.   A light emitting element provided with the organic thin film of Claim 17.   A planar light source comprising the light emitting device according to claim 18.   A display device comprising the light emitting device according to claim 18.